Lubricating oil compositions with performance improvement of viscosity modifiers for ethylene-propylene copolymers with syndiotactic-based propylene

Abstract

The invention provides a lubricating oil composition comprising a major amount of a lubricant base oil and a minor amount of a viscosity index improver, the viscosity index improver comprising an ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 wt% to 20 wt% ethylene; b) 80 wt% to 98 wt% propylene; c) 50% to 99% rr triads; and d) Mw(LS) of 10 kg / mol to 250 kg / mol.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 63 / 276,025, filed November 5, 2021, entitled “Performance Improvement of Lubricating Oil Compositions with Viscosity Modifiers for Ethylene-Propylene Copolymers Based on Syndiotactic Propylene,” the disclosure of which is hereby incorporated by reference for all purposes under 35 U.S.C. § 119(e). TECHNICAL FIELD

[0003] The present disclosure relates to ethylene-propylene copolymers based on syndiotactic propylene in lubricating oils and uses thereof. BACKGROUND

[0004] Applying a lubricating fluid between moving surfaces can reduce friction, thereby improving efficiency and reducing wear. Lubricating fluids also generally function to dissipate heat generated by friction between moving surfaces.

[0005] One type of lubricating fluid is petroleum-based lubricating oil for internal combustion engines. Lubricating oils contain additives that help the lubricating oil to have a certain viscosity at a given temperature. Generally, the viscosity of lubricating oils and lubricating fluids is inversely proportional to temperature. When the temperature of a lubricating fluid increases, the viscosity typically decreases, and when the temperature decreases, the viscosity typically increases. For example, for internal combustion engines, it is desirable to have a lower viscosity at low temperatures to facilitate engine start-up in cold weather, while having a higher viscosity at higher ambient temperatures where lubricating performance generally decreases.

[0006] Additives for lubricating fluids and oils include rheology modifiers, such as viscosity index improvers (VII). Viscosity index improver components, many of which are from olefin copolymers, can change the rheological behavior of the lubricant, thereby increasing the viscosity and promoting a more constant viscosity over the temperature range in which the lubricant is used.

[0007] Ideal Vlls generally exhibit sufficiently low viscosity properties at low temperatures, so that the lubricating fluid containing the Vll can maintain sufficiently low viscosity at low temperatures, which can be evidenced by fluid measurements such as pour point, Mini Rotary Viscometer (MRV), and Cold Cranking Simulator (CCS) tests. In addition, it can be desirable to maximize thickening efficiency (TE), which is a measure of the thickening ability of the polymer in the lubricating fluid (e.g., a greater TE indicates that a lesser amount of Vll is needed to achieve the desired performance). One challenge is that TE and Shear Stability Index (SSI) are interdependent, and different grades of lubricating oil and target end uses and / or markets can have different SSI requirements for various Vlls. Desirable Vlls are those that provide a higher thickening efficiency (TE) at a given target or required SSI (again, the required SSI can be different for different target uses). This means that, for a given SSI, ideal Vlls should be designed to increase or maximize TE at a given SSI.

[0008] As explained in U.S. Patent No. 9,139,794 and U.S. Patent No. 9,127,151 (see, e.g., ‘151 at col. 5, lines 21-32), it is generally believed that the composition of the olefin copolymer Vll at a given SSI largely determines the TE, with higher ethylene content being preferred because of its higher TE. On the other hand, the ‘151 patent explains that while increasing the ethylene content of the rheology modifier increases the TE / SSI ratio, it also results in an increase in the crystallinity of the olefin copolymer, which is believed to be detrimental because the crystalline polymer tends to associate. These associations apparently manifest as high viscosity regions (e.g., “lumps”), which make the oil appearance non-uniform. Thus, in designing the olefin copolymer Vll, it appears that a trade-off must be made. In order to achieve a greater TE, one must accept a higher crystallinity, thereby sacrificing low temperature performance due to, for example, a stronger tendency to gel and / or an undesirable higher SSI. In fact, many commercial viscosity modifiers based on ethylene-propylene copolymers use an ethylene content below 50%, such that the final polymer does not exhibit a melting point that is a solid or non-uniform appearance in the lubricating oil composition.

[0009] This perceivable trade-off can make certain olefin copolymers VII difficult to achieve the desired properties. In the past, propylene-based polymers and copolymers have been used as viscosity index improvers, as described in WO Patent Application Publication 2016 / 018523 Al and U.S. Patent Application Publication No. 2012 / 0015854 Al. Propylene-based copolymers include propylene as the main monomer and units derived from one or more other alpha-olefins, such as ethylene. Due to low crystallinity, these viscosity modifiers have proven to generally have lower thickening ability compared to olefin copolymers with an ethylene content of 50% or more. Thus, there is a need for viscosity index improvers and lubricating oils comprising propylene-based copolymers that exhibit good measured viscosity, high thickening efficiency, and good low temperature properties. Furthermore, it can be particularly advantageous to use propylene-based ethylene-propylene copolymers with low ethylene content to determine the desired VII. SUMMARY

[0010] The present disclosure addresses the ongoing need to develop viscosity index improvers and lubricating oils. More specifically, the present disclosure provides ethylene-propylene copolymers based on syndiotactic propylene that exhibit good measured viscosity, high thickening efficiency, and good low temperature properties. It has been surprisingly found that the tacticity of the propylene segments in the ethylene-propylene copolymers plays an important role in the performance of the viscosity index improver and lubricating oil compositions.

[0011] The present disclosure relates to a lubricating oil composition comprising an ethylene-propylene copolymer based on syndiotactic propylene having a) 2 wt% to 20 wt% ethylene; b) 80 wt% to 98 wt% propylene; c) 50% to 99% rr triads; and d) 10 kg / mol to 250 kg / mol Mw(LS).

[0012] In another aspect, the present disclosure relates to a method of making a lubricating oil composition with improved low temperature properties, the method comprising: mixing a lubricant base oil and 0.01 wt% to 20 wt% of a viscosity index improver, wherein the viscosity index improver comprises an ethylene-propylene copolymer based on syndiotactic propylene having a) 2 wt% to 20 wt% ethylene; b) 80 wt% to 98 wt% propylene; c) 50% to 99% rr triads; and d) 10 kg / mol to 250 kg / mol Mw(LS), and wherein the lubricant base oil has a kinematic viscosity at 100°C of 1.4-20 mm 2 / s.

[0013] In yet another aspect, the present disclosure relates to a method of lubricating an engine comprising: supplying to the engine a lubricating oil composition comprising: a major amount of a base oil of lubricating viscosity; an ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 wt.% to 20 wt.% ethylene; b) 80 wt.% to 98 wt.% propylene; c) 50% to 99% rr triads; and d) 10 kg / mol to 250 kg / mol Mw(LS), and wherein the lubricant base oil has a kinematic viscosity at 100°C of 1.4 to 20 mm 2 / s. DETAILED DESCRIPTION

[0014] For the purposes of this specification and the claims thereto, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is in its polymerized form. For example, when a copolymer is said to have an “ethylene” content of 2 wt.% to 20 wt.%, it is understood that the monomer (“mer”) units in the copolymer are derived from ethylene in the polymerization reaction, and that said derived units are present in an amount of 2 wt.% to 20 wt.% based on the weight of the copolymer.

[0015] A “polymer” has two or more monomer (“mer”) units, which are the same or different. A “homopolymer” is a polymer having the same mer units. A “copolymer” is a polymer having two or more different mer units from each other.

[0016] As used herein, the term “substituted” means that a hydrogen group is replaced by a heteroatom or a heteroatom-containing group. For example, a “substituted hydrocarbyl” is a group consisting of carbon and hydrogen in which at least one hydrogen is replaced by a heteroatom or a heteroatom-containing group.

[0017] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt.% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined by Mw divided by Mn. Unless otherwise specified, all molecular weight units (such as Mw, Mn, Mz) are g / mol.

[0018] Generally, olefin polymers and oligomers (“polyolefins” or “polyolefin polymers”), particularly poly-alpha-olefin polymers comprising propylene or other C3 or higher alpha-olefin monomers, contain branched hydrocarbyl groups on the polymer backbone. The branched hydrocarbyl groups can be arranged in different stereochemical configurations relative to the polymer backbone. These arrangements include atactic configurations, isotactic configurations, and / or syndiotactic configurations.

[0019] As used herein, the "stereoregularity" of a polymer reflects the stereochcmical regularity of the branched hydrocarbyl groups on the polymer molecular backbone. Achievable stereoregularity can be related to the crystallinity of olefin polymers, particularly polyalpha-olefin polymers. Three main types of stereoregularity have been described for polyalpha-olefins: atactic, isotactic, and / or syndiotactic.

[0020] Atactic polyolefins refer to those in which the branched hydrocarbyl groups on the polymer molecular backbone exhibit no regular order with respect to the backbone. This random or atactic structure is manifested by a polymer backbone composed of alternating methylene and methine carbons, and randomly oriented pendant substituent methine carbons. The methine carbons randomly have Rectus ("R") and Sinister ("S") configurations, forming adjacent pairs of like configurations ("meso" or "m" dyads) or different configurations ("racemic" or "r" dyads).

[0021] Isotactic polyolefins are characterized by having branched hydrocarbyl groups that are spatially ordered on the same side or plane of the polymer backbone. Using isotactic polypropylene as an example, the isotactic structure is generally described as having branched methyl groups attached to the tertiary carbon atoms of successive monomer units on the same side of an imaginary plane through the polymer carbon backbone chain, e.g., the methyl groups are all located above or below the plane. The percentage of m dyads in the chain determines the isotacticity of the polymer and is related to the crystallinity of the polymer.

[0022] Syndiotactic polyolefins refer to those in which the branched hydrocarbyl groups on the polymer molecular backbone are sequentially and alternately ordered from one side or plane to the opposite side or plane of the polymer backbone. The percentage of r dyads in the chain determines the syndiotacticity of the polymer and is related to the crystallinity of the polymer.

[0023] The molecular chain backbone of a syndiotactic polymer can be viewed as an olefin copolymer having alternating stereochemical configurations. Highly syndiotactic polymers can be highly crystalline and, thus, can have a definite melting point similar to its isotactic polymorph, and can be characterized in part by its melting point temperature.

[0024] The tacticity of a triad of a polymer refers to the relative tacticity of a sequence of three adjacent propylene units, which is a chain consisting of head to tail linkages, represented as a binary combination of m and r sequences. For propylene-based polymers, it is typically expressed as the ratio of the number of units of a specified tacticity in the polymer to all propylene triads. For example, a rr triad represents 3 adjacent propylene units in which the stereochemistry of the propylene units is alternating (e.g., RSR, SRS).

[0025] The tacticity of the ethylene-propylene copolymer is measured by 13 C NMR (concentration of isotactic and syndiotactic diads ([m] and [r]) and triads ([mm], [mr], and [rr])) is measured. The designation "m" or "r" indicates the stereochemistry of a pair of consecutive propylene groups, "m" indicates meso, and "r" indicates racemic. The calculations involved in characterizing polymers by NMR are described in F. A. Bovey, Polymer Conformation and Configuration (Academic Press, New York 1969) and in J. Randall, Polymer Sequence Determination, (Academic Press, New York 1977). 13 C-NMR Method (Academic Press, New York, 1977).

[0026] The "tacticity index of rr triads" of a polymer is a measure of the relative syndiotacticity of a sequence of three adjacent propylene units connected in head to tail configuration. More specifically, in the present invention, the tacticity index of rr triads (also referred to as "rr fraction") of a polypropylene copolymer is expressed as the ratio of the number of units of racemic tacticity to all methyl triads in the copolymer:

[0027]

[0028] The regions of PP+EP (mm), PP+EP (mr), and PP+EP (rr) are defined as

[0029] Chemical shift range (ppm) PP + EP (mm) 21.2-22.3 PP + EP (mr) 20.4-21.2 PP + EP (rr) 19.6-20.4

[0030] This tacticity calculation of triads does not take into account the sequences, chain ends, or defects in the region that exist within these regions.

[0031] Similarly, the calculation of m diads and r diads is as follows, where mm, mr, and rr are defined as above:

[0032] m = mm + 1 / 2 mr

[0033] r = rr + 1 / 2mr

[0034] 13 C NMR can be used to determine the monomer content and sequence distribution of ethylene-propylene copolymers using procedures adapted from a paper by J.C. Randall (Polymer Reviews, 1989, vol. 29(2), pp. 201-317). This paper includes the measurement and calculation of 1,2-propylene addition triad sequence distribution (referred to as EEE, EEP, PEP, EPE, EPP, and PPP, respectively) and is reported in mole fraction.

[0035] The present disclosure relates to ethylene-propylene copolymers based on syndiotactic propylene in lubricating oils and uses thereof. The ethylene-propylene copolymers based on syndiotactic propylene are capable of improving the performance of lubricating oils, such as good measured viscosity, high thickening efficiency, and good low temperature performance.

[0036] According to one embodiment, the ethylene-propylene copolymers based on syndiotactic propylene used in the lubricating oil compositions of the present disclosure comprise: ethylene-propylene copolymers based on syndiotactic propylene having a) 2 wt% to 20 wt% of ethylene; b) 80 wt% to 98 wt% of propylene; c) 50% to 99% of rr triads; and d) Mw(LS) of 10 kg / mol to 250 kg / mol.

[0037] In some embodiments, the ethylene-propylene copolymers based on syndiotactic propylene comprise 4 wt% to 18 wt% of ethylene, 5 wt% to 15 wt% of ethylene, 6 wt% to 12 wt% of ethylene, 7 wt% to 9 wt% of ethylene.

[0038] In some embodiments, the ethylene-propylene copolymers based on syndiotactic propylene comprise 82 wt% to 96 wt% of propylene, 85 wt% to 95 wt% of propylene, 88 wt% to 94 wt% of propylene, 91 wt% to 93 wt% of propylene.

[0039] In one embodiment, the syndiotactic-rich ethylene-propylene copolymers prepared herein have stereoregular propylene crystallinity with syndiotactic. As used herein, the term “stereoregular” means that in a polymer chain that does not contain any other monomers such as ethylene, a major amount (i.e., greater than 50%) of propylene residues in the polypropylene segment have the same 1,2 insertion, and the stereochemical orientation of the branching methyl groups is the same, which can be meso or racemic.

[0040] The propylene copolymers prepared herein can have a Mw(LS) of 10 kg / mol to 250 kg / mol, 20 kg / mol to 200 kg / mol, 30 kg / mol to 150 kg / mol, 40 kg / mol to 100 kg / mol, 50 kg / mol to 90 kg / mol, 60 kg / mol to 80 kg / mol, 65 kg / mol to 75 kg / mol, or 70 kg / mol to 75 kg / mol. 13The ethylene-propylene copolymers may have a tacticity index of rr triads of three propylene units of 55% or greater, 60% or greater, 65% or greater, or 70% or greater as measured by C NMR. In some embodiments, the ethylene-propylene copolymers based on syndiotactic propylene may have 60% to 90% rr triads, 65% to 90% rr triads, 70% to 90% rr triads, 75% to 90% rr triads, and 80% to 90% rr triads. In other embodiments, the copolymers may have 65% to 85% rr triads, and 70% to 80% rr triads.

[0041] In some embodiments, the Mw(LS) can range from 20 to 150 kg / mol, 30 to 140 kg / mol, 40 to 120 kg / mol, 50 to 100 kg / mol, and 60 to 90 kg / mol.

[0042] The present disclosure includes syndiotactic propylene-based ethylene-propylene copolymers having an MFR of 0.1 to 450 g / 10 min, as measured at 2.16 kg and 230° C. The MFR, as measured at 2.16 kg and 230° C., can be 1 to 400 g / 10 min, 10 to 300 g / 10 min, 50 to 200 g / 10 min, and 75 to 150 g / 10 min.

[0043] The syndiotactic propylene-based ethylene-propylene copolymer used in the lubricating oil composition of the present disclosure may be prepared by any suitable means known in the art.

[0044] In some embodiments, the glass transition temperature of the syndiotactic-rich ethylene-propylene copolymer is 20°C or less, or 10°C or less, or 0°C or less, or -5°C or less, or -10°C or less. In another embodiment, the relationship between the Tg (°C) from DSC and the ethylene content (C2 wt%) from FTIR of the syndiotactic-rich ethylene-propylene copolymer is -0.5263*T g -4.8158 <C2重量%<-0.5714*T g +0.9857.

[0045] In some embodiments, the syndiotactic-rich ethylene-propylene copolymer does not exhibit a distinct melting peak with a heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10 °C / min. In some embodiments, the syndiotactic-rich ethylene-propylene copolymer does not exhibit an endothermic peak in the second heating cycle of a DSC measurement at a scan rate of 10 °C / min. Alternatively, the syndiotactic-rich ethylene-propylene copolymer does not have a melting peak in the second heating cycle of a DSC measurement according to the procedure described herein.

[0046] In embodiments where the syndiotactic-rich ethylene-propylene copolymer is a blended polymer. The tacticity index of the rr triads of the first polymer component can be 70% or less, 65% or less, or even 60% or less. The tacticity index of the rr triads of the second polymer component can be 70% or more, 75% or more, or even 80% or more.

[0047] In embodiments where the syndiotactic-rich ethylene-propylene copolymer is a blended polymer, the first syndiotactic-rich ethylene-propylene copolymer component can have an ethylene content of less than 10 wt%, or less than 7 wt%, or less than 5 wt%, or less than 3 wt%, based on the total weight of the first polymer component. The second syndiotactic-rich ethylene-propylene copolymer component can have an ethylene content of greater than 5 wt%, or greater than 7 wt%, or greater than 10 wt%, or greater than 15 wt%, or greater than 20 wt%, and up to 25 wt%, based on the total weight of the second polymer component.

[0048] In embodiments, the weight average molecular weight of the first copolymer component is greater than the weight average molecular weight of the second copolymer component. In embodiments, the weight average molecular weight of the first copolymer component is greater than about 150,000 g / mol, or about 200,000 g / mol, or about 250,000 g / mol. Alternatively, the weight average molecular weight of the second copolymer component is less than about 150,000 g / mol, or about 100,000 g / mol, or about 50,000 g / mol to less than about 20,000 g / mol.

[0049] According to various embodiments, the syndiotactic-rich ethylene-propylene copolymer can be a blend of at least two syndiotactic-rich ethylene-propylene copolymers. In one embodiment of the present application, the blend has a bimodal or broad molecular weight distribution (MWD > 3.0). The blend can also have a bimodal or broad composition distribution. Alternatively, one component has an ethylene content ranging from 0.2 wt% to 5 wt% and a Mw ranging from 100,000 g / mol to 400,000 g / mol; another component has an ethylene content ranging from 2 wt% to 15 wt% and a Mw ranging from 10,000 g / mol to 150,000 g / mol.

[0050] Catalyst

[0051] The syndiotactic-based propylene ethylene-propylene copolymers of the present disclosure can be prepared by any suitable catalyst known in the art. The catalyst compounds described herein are used to polymerize olefinic monomers including propylene and ethylene to form syndiotactic-based propylene ethylene-propylene copolymers. As used herein, the terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" are used interchangeably within the present disclosure. Likewise, the terms "group," "radical," and "substituent" are also used interchangeably within the present disclosure. For the purposes of the present disclosure, "hydrocarbyl group" is defined to be a C1-C100 group, and can be linear, branched, or cyclic. When cyclic, the hydrocarbyl group can be aromatic, or non-aromatic. "Hydrocarbyl group" is defined to include substituted hydrocarbyl groups, halocarbyl groups, substituted halocarbyl groups, silylcarbyl groups, and germylcarbyl groups, as defined below. Substituted hydrocarbyl groups are groups in which at least one hydrogen atom has been replaced with at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or in which at least one non-hydrocarbon atom or group has been inserted, such as — O —, — S —, — Se —, — Te —, — N(R*) —, ═N—, — P(R*) —, ═P—, — As(R*) —, ═As—, — Sb(R*) —, ═Sb—, — B(R*) —, ═B—, — Si(R*)2—, — Ge(R*)2—, — Sn(R*)2—, — Pb(R*)2—, and the like, within hydrocarbyl groups, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring structure.

[0052] Halocarbyl groups are groups in which one or more of the hydrocarbyl hydrogens has been replaced with at least one halogen (such as F, Cl, Br, I) or halogen-containing group (such as CF3).

[0053] A substituted halocarbyl group is a group in which at least one halocarbyl group hydrogen atom or halogen atom is replaced by at least one functional group (such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like) or in which at least one non-carbon atom or group (such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like) is inserted within the halocarbyl group, wherein R* is independently a hydrocarbyl or halocarbyl group, provided that at least one halogen atom remains on the original halocarbyl group. Additionally, two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring-structure.

[0054] A hydrocarbylsilyl group, also known as a silylcarbyl group (also known as a hydrocarbyl silyl group), is a group in which one or more hydrocarbyl hydrogen atoms are replaced by at least one SiR*3-containing group, or in which at least one -Si(R*)2- is inserted within the hydrocarbyl group, wherein R* is independently hydrogen, a hydrocarbyl, or a halocarbyl group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring-structure. The silylcarbyl group can be bound through a silicon or carbon atom.

[0055] A substituted silylcarbyl radical is a silylcarbyl radical in which at least one hydrogen atom has been replaced with at least one functional group, such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR*3, and the like, or in which at least one non-hydrocarbon atom or group, such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like, is inserted in the silylcarbyl radical. In these radicals, R* independently is hydrogen, a carbyl or hydrocarbyl group as previously defined, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring structure.

[0056] A germylcarbyl radical, also referred to as a germylcarbyl group (also germylcarbyl group), is a radical in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one GeR*3-containing group, or in which at least one -Ge(R*)2- is inserted in the hydrocarbyl radical. In these radicals, R* independently is hydrogen, a carbyl or hydrocarbyl group as previously defined, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring structure. The germylcarbyl radical can be bonded through a Ge or a C atom.

[0057] A substituted methylgermylalkyl group is a methylgermylalkyl group in which at least one hydrogen atom is replaced by at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR*3, and the like, or a methylgermylalkyl group in which at least one non-hydrocarbon atom or group such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like is inserted within the methylgermylalkyl group, where R* is independently hydrogen, a hydrocarbyl group, or a halocarbyl group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0058] A "polar radical" (or "polar group") is a group in which a heteroatom functionality is directly bonded to one or more of the indicated atoms. Polar radicals include heteroatoms in Groups 1-17 of the Periodic Table of the Elements (excluding carbon and hydrogen), which can exist alone or be linked to other elements through covalent bonds or other interactions such as ionic bonds, van der Waals forces, or hydrogen bonds. Examples of groups containing functional heteroatoms include carboxylic acids, acid halides, carboxylic esters, carboxylic salts, carboxylic anhydrides, aldehydes and their chalcogen (Group 14) analogs, alcohols and phenols, ethers, peroxides and hydroperoxides, carboxylic amides, hydrazides and imides, amidines and other nitrogen-containing analogs of amides, nitriles, amines and imines, azo, nitro, other nitrogen-containing compounds, sulfuric acid, selenic acid, mercaptans, sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphorus-containing compounds, silanes, boranes, borates, alanes, aluminates. Examples of polar radicals include NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SnR*3, PbR*3, and the like, where R* is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl group as defined above, and two R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0059] In using the terms "substituted or unsubstituted cyclopentadienyl ligand," "substituted or unsubstituted indenyl ligand," and "substituted or unsubstituted tetrahydroindenyl ligand," the substituents of the above ligands can be hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl. Substitution can also occur on the ring with heterocyclopentadienyl ligands, heteroindenyl ligands, or heterotetrahydroindenyl ligands, wherein each ligand must also be substituted or unsubstituted.

[0060] The hydrocarbyl groups can be independently selected from the group consisting of methyl, ethyl, ethenyl, and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosenynyl, heneicosenynyl, docosenynyl, tricosenynyl, tetracosenynyl, pentacosenynyl, hexacosenynyl, heptacosenynyl, octacosenynyl, nonacosenynyl, triacontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, and decadienyl. Also included are isomers of saturated, partially unsaturated, and aromatic and polycyclic structures, where the groups can additionally be substituted as described above. Examples include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl, methylbenzyl, naphthyl, anthryl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbornyl, norbornenyl, adamantyl, and the like. For the present disclosure, when a group is listed, it represents that group type and all other groups formed from that group type upon substitution as defined above. The listed alkyl, alkenyl, and alkynyl groups include all isomers, including cyclic isomers where appropriate, e.g., butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, and cyclobutyl (as well as similar substituted cyclobutyl and cyclopropyl groups); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (as well as similar substituted cyclobutyl and cyclopropyl groups); butenyl includes 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (as well as cyclobutenyl and cyclopropenyl) in E and Z forms.Cyclic compounds with substituents include all isomeric forms, e.g., methylphenyl includes o-methylphenyl, m-methylphenyl, and p-methylphenyl; dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0061] Examples of cyclopentadienyl and indenyl ligands are shown below as anionic ligands. The numbering scheme for the ring is also shown. When the cyclopentadienyl ligand has one bridging substituent, the bridging substituent is at position 1. When the cyclopentadienyl ligand has two bridging substituents, the bridging substituents are at positions 1 and 2. When the fluorenyl ligand has a bridging substituent, the bridging substituent is at position 9. When the dibenzo[b,h]fluorene has a bridging substituent, the bridging substituent is at position 12.

[0062]

[0063] As shown in the following figure, heterocyclopentapentalenyl, heterofluorenyl, and the like also use similar numbering and nomenclature. Each structure shown is an anion.

[0064] Non-limiting examples of heterocyclopentapentalenyl groups include the following, where Q represents a heteroatom O, S, Se, or Te, or a heteroatom group NR**, PR**, AsR**, or SbR**, where R** is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl substituents. When the heterocyclopentapentalenyl ligand has a bridging substituent, the bridging substituent is at position 7.

[0065]

[0066] Non-limiting examples of heterofluorenyl groups include the following, where Z represents a heteroatom N or P. When the heterofluorenyl ligand has a bridging substituent, the bridging substituent is at position 9.

[0067]

[0068] A "ring heteroatom" is a heteroatom located on a ring structure of a ring. A "heteroatom substituent" is a group containing a heteroatom that is directly bonded to a ring structure through the heteroatom. A "bridging heteroatom substituent" is a heteroatom or a heteroatom group that is directly bound to two different ring structures through the heteroatom. The terms "ring heteroatom," "heteroatom substituent," and "bridging heteroatom substituent" are shown below, where Z and R' are as defined above.

[0069]

[0070] "Ring carbon atom" means a carbon atom that is part of a ring structure that is cyclic. For example, an indenyl ligand has nine ring carbon atoms; a cyclopentadienyl ligand has five ring carbon atoms.

[0071] Transition metal compounds have symmetry elements and belong to a symmetry group. These elements and groups are well established and can be found in Chemical Applications of Group Theory (2nd Edition) by F. Albert Cotton, Wiley-Interscience, 1971. A compound with C s A compound with symmetry has a mirror plane. For example, the C s The mirror plane bisects the zirconium center, the carbon bridge, the cyclopentadienyl ligand, and the fluorenyl ligand.

[0072]

[0073] A symmetry substituent is a substituent that preserves the C s symmetry of the transition metal. For example, a t-butyl group substituted at the 2 and 7 positions of a fluorenyl ligand is a symmetry substituent.

[0074] A compound with quasi-C s symmetry is similar to a compound with C s symmetry, but does not include the bridging group, labile ligand, and ring size similar remote substituents on the cyclopentadienyl ligand or fluorenyl ligand when determining the symmetry of the compound. These compounds, while not truly C s symmetric, are considered to have a C s symmetric active site for olefin polymerization, given the appropriate retained ligand structure. Thus, for example, a compound with a MeEtSi or MePhSi bridging ligand is considered to have a quasi-C s symmetric plane, given the appropriate retained ligand structure. Likewise, for example, a compound with one Me ligand and one Cl labile ligand is considered to have a quasi-C s symmetric plane, given the appropriate retained ligand structure. The following are non-limiting examples of quasi-C s symmetric compounds:

[0075]

[0076] A compound with quasi-C sSymmetrical compounds can also have different substituents on the non-labile ligand (i.e., the cyclopentadienyl or fluorenyl ligand). This type of substituent is referred to as a quasi-symmetrical substituent, and is typically adjacent to the bridging group and is not substantially different in size from the other. Typically, the difference in size of these substituents is within 2 non-hydrogen atoms of each other. Thus, a cyclopentadienyl group substituted with a methyl group at the 2 position and an ethyl group at the 5 position, or a cyclopentadienyl group substituted with a methyl group at the 2 position and no substituent at the 5 position, or a fluorenyl group substituted with a hexyl group at the 1 position and an octyl group at the 8 position, are all considered to have quasi-C s symmetry.

[0077] In general, those catalysts that are capable of producing syndiotactic polypropylene and that are capable of reacting with hydrogen to terminate growing polymer chains are catalysts that are useful in the production of the syndiotactic polypropylene homopolymers and the syndiotactic-based propylene ethylene-propylene copolymers described herein.

[0078] Catalysts useful in the production of syndiotactic polypropylene homopolymers and syndiotactic-rich propylene-based ethylene-propylene copolymers include metallocene compounds (pre-catalysts) having a structure represented by formula (1) having C s or quasi-C s symmetry:

[0079]

[0080] wherein:

[0081] M is zirconium or hafnium;

[0082] L 1 is an unsubstituted fluorenyl, heterocyclopentadienyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentadienyl, or heterofluorenyl ligand having one or more symmetrical or quasi-symmetrical substituents, each substituent group being independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group, optionally two or more adjacent substituents can be joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic ring- or poly-ring-structure;

[0083] L 2 is a cyclopentadienyl ring or substituted cyclopentadienyl ring having one or more symmetrical or quasi-symmetrical substituents at the 2 and 5 positions of the ring, each substituent group being independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group;

[0084] G is a bridging group;

[0085] each X is independently a hydride group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, a silylcarbyl group, or a germylcarbyl group; or two Xs are joined and bound in a 2 electron donor ancillary ligand to the metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms; or two Xs can together be an olefinic or diene, or aryne ligand; two Xs independently can be halogen, alcoholate, aryloxy, amide, phosphide, or other univalent anionic ligand, or two Xs can also be joined to form a dianionic chelating ligand.

[0086] In some embodiments of formula (1), L 1 is fluorenyl or substituted fluorenyl; for example, fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, 2,7-di-t-butylfluorenyl, or 1,1,4,4,7,7,10,10-octamethyl- octahydrofluorenyl. Most preferred is 2,7-di-t-butylfluorenyl, or fluorenyl. In some embodiments, L 2 is cyclopentadienyl. In some embodiments, G is methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, or di(p-triethylsilylphenyl)methylene, most preferably dimethylmethylene, diphenylmethylene, or di(p-triethylsilylphenyl)methylene. In some embodiments, each X is independently a hydrocarbyl or halogenated group, such as methyl, benzyl, fluoro, or chloro. In some embodiments, M is preferably zirconium. In alternative embodiments, M is hafnium.

[0087] A subset of metallocene compounds (pre-catalysts) represented by formula (1) that can be used having C s or quasi-C s symmetry are represented by formula (1a):

[0088]

[0089] wherein

[0090] M, G, and X are as defined in formula (1);

[0091] each R a and R bare independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl, germylhydrocarbyl, or a polar group, and optionally, two or more adjacent substituents may be linked to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent, provided that each R a and each R b The same so that the compound is C s Symmetrical or Quasi-C s Symmetrical;

[0092] Each R c are independently symmetrical or quasi-symmetrical substituents with respect to one another and are selected from hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl, or germylhydrocarbyl group;

[0093] Each R d are symmetrical or quasi-symmetrical substituents with respect to one another and are independently selected from hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl, or germylhydrocarbyl group.

[0094] In some embodiments of Formula (1a), each R d 、R a and R c is hydrogen, and each R b is hydrogen, hydrocarbon, halogen, silyl hydrocarbon, or a polar group; such as hydrogen, methyl, ethyl, propyl, butyl, phenyl, such as hydrogen or butyl; such as hydrogen or tert-butyl; such as tert-butyl.

[0095] In other embodiments of formula (1a), each R d 、R b and R c is hydrogen, and each R a is independently hydrogen, hydrocarbyl, halogen, or silylhydrocarbyl; such as hydrogen, methyl, ethyl, propyl, butyl, fluoro, chloro, or bromo; such as hydrogen or butyl; such as hydrogen or tert-butyl; such as hydrogen.

[0096] In still other embodiments of formula (1a), each R d and R c are hydrogen, each R a and R b Connected together to form a fused partially saturated six-membered carbon ring, each of which may be substituted with four methyl substituents. The ligand structure is shown in formula (1b):

[0097]

[0098] In still other embodiments of formula (1a), R c and R d is hydrogen; each R a and R b are independently hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl or phenyl, such as R a is hydrogen, R b is hydrogen, methyl, ethyl, propyl or butyl; or R b is hydrogen, R a is hydrogen, methyl, ethyl, propyl or butyl. a is hydrogen, R b is tert-butyl or hydrogen. G can be methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, diphenylsilylene, bis(4-triethylsilylphenyl)silylene, ethylene, bis(p-triethylsilylphenyl)methylene, such as diphenylmethylene, dimethylmethylene, diphenylsilylene, and dimethylsilylene; such as diphenylmethylene. Each X is independently a hydrocarbon group or a halide, such as methyl, benzyl, fluoro, or chloro, such as methyl or chloro. In some embodiments, M is zirconium. In other embodiments, M is hafnium.

[0099] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1), (1a) and / or (1b), M is zirconium.

[0100] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1), (1a) and / or (1b), X is methyl.

[0101] In some embodiments of Formula (1a), each R d 、R a and R c is hydrogen, and each R b It is methyl, ethyl, propyl, or butyl, with tert-butyl being the most preferred.

[0102] In some preferred embodiments of the present invention, for the metallocene compounds of formula (1a) and / or (1b), G is bis(p-triethylsilylphenyl)methylene.

[0103] Examples of pre-catalysts represented by formula (1) can include: diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, methylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, ethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, methylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, diphenylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, ethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, bis(p-trimethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, methylene-(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, ethylene-(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, methylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, dimethylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, dimethylsilylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, diphenylsilylene-(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, ethylene-(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, and bis(p-trimethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)hafnium dimethyl. In some embodiments, the pre-catalyst represented by formula (1) can be diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, bis(p-trimethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, or bis(p-trimethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl. In some embodiments, zirconium-based catalysts of formula 1, 1a, and 1b are preferred, such as diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl or bis(p-trimethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl.

[0104] Catalysts capable of producing syndiotactic polypropylene homopolymers and ethylene-propylene copolymers based on syndiotactic-rich propylene can also include metallocene compounds (pre-catalysts) having a structure represented by formula (2) having C s or quasi-C s symmetry:

[0105]

[0106] wherein:

[0107] M is hafnium, zirconium, or titanium;

[0108] L 1 is an unsubstituted fluorenyl, heterocyclopentadienyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentadienyl, or heterofluorenyl ligand having one or more symmetric or quasi-symmetric substituent groups, each substituent group independently being a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group, optionally two or more adjacent substituents can be joined to form a substituted or unsubstituted saturated, or partially unsaturated, or aromatic ring structure;

[0109] G is a bridging group;

[0110] J is a heteroatom from Group 15, such as N or P, such as N;

[0111] R' is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl group;

[0112] L' is a neutral Lewis base, w represents the number of L' bound to M, where w is 0, 1, or 2, optionally L' and any X can be arbitrarily interlinked;

[0113] each X is independently a hydride group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, a germylcarbyl group, or a substituted germylcarbyl group; or two X are joined and bound to the metal atom to form a metallocycle ring containing about 3 to about 20 carbon atoms; or two X together can be an olefinic, diene, or aryne ligand; two X can independently be halogen, alcoholate, aryloxy, amide, phosphide, or other univalent anionic ligand, or two X can also be joined to form a dianionic chelating ligand.

[0114] In some embodiments of formula (2), L 1fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, or 1,1,4,4,7,7,10,10-octamethyl- octahydrodibenzofluorenyl. In some embodiments, G is methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, methylphenylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, such as diphenylmethylene, diphenylsilylene, methylphenylsilylene, and dimethylsilylene; such as dimethylsilylene. In some embodiments, J is nitrogen. In some embodiments, R' is hydrocarbyl or halocarbyl, such as C3-C 20 hydrocarbyl, such as all isomers (including cyclic and polycyclic) of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, benzyl, phenyl, and substituted phenyl, such as t-butyl, neopentyl, benzyl, phenyl, diisopropylphenyl, adamantyl, norbornyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl, such as t-butyl, adamant-1-yl, norborn-2-yl, cyclohexyl, cyclooctyl, and cyclododecyl. In some embodiments, X is hydrocarbyl or halogenated, such as methyl, benzyl, fluoro, or chloro, such as methyl or chloro. In some embodiments, w is 0 (L' is absent), M is zirconium or titanium.

[0115] In some embodiments, the catalyst of formula (2) is:

[0116]

[0117] The catalysts for preparing syndiotactic polypropylene homopolymers and ethylene-propylene copolymers based on syndiotactic-rich propylene can also include a metallocene compound (pre-catalyst) having a structure represented by formula (3) having C s or quasi-C s symmetry:

[0118]

[0119] wherein:

[0120] M is hafnium or zirconium;

[0121] L 3 is a cyclopentadienyl ring optionally substituted at the 4-position with a group selected from hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl groups;

[0122] L 4 is a substituted cyclopentadienyl ring having symmetric or quasi-symmetric substituents at the 3 and 5 positions of the ring, each substituent group independently being a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group;

[0123] G' and G" are bridging groups;

[0124] each X is independently a hydride group, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group; or two X are joined and bound to the metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms; or two X together can be an olefinic, diene, or aryne ligand; two X can independently be halogen, alcoholate, aryloxy, amide, phosphide, or other univalent anionic ligand, or two X can also be joined to form a dianionic chelating ligand.

[0125] In formula (3), L 3 is cyclopentadienyl, or cyclopentadienyl substituted at the 4 position of the cyclopentadienyl ring with a hydrocarbyl or silylcarbyl group, such as cyclopentadienyl, 4-methylcyclopentadienyl, 4-ethylcyclopentadienyl, 4-propylcyclopentadienyl, 4-butylcyclopentadienyl, 4-pentylcyclopentadienyl, 4-hexylcyclopentadienyl, 4-heptylcyclopentadienyl, 3-octylcyclopentadienyl, or 4-trimethylsilylcyclopentadienyl, such as cyclopentadienyl, 4-isopropylcyclopentadienyl, 4-t-butylcyclopentadienyl, 4-(2,2-dimethylpent-3-yl)cyclopentadienyl, 4-(2,2-dimethylbut-3-yl)cyclopentadienyl, or 4-trimethylsilylcyclopentadienyl, such as cyclopentadienyl, 4-isopropylcyclopentadienyl, or 4-trimethylsilylcyclopentadienyl. In some embodiments, L 4hydrocarbyl or silylhydrocarbyl substituted at the 3 and 5 positions of the cyclopentadienyl ring, such as 3,5-dimethylcyclopentadienyl, 3,5-diethylcyclopentadienyl, 3,5- dipropylcyclopentadienyl, 3,5-dibutylcyclopentadienyl, 3,5-dipentylcyclopentadienyl, 3,5- dihexylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl, such as 3,5-dimethylcyclopentadienyl, 3,5-diisopropylcyclopentadienyl, 3,5-di-tert- butylcyclopentadienyl, 3,5-dicyclopentylcyclopentadienyl, 3,5-dipent-3-ylcyclopentadienyl, 3,5- dicyclohexylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl, such as 3,5-dimethylcyclopentadienyl, 3,5-diisopropylcyclopentadienyl, 3,5-di-tert- butylcyclopentadienyl, 3,5-dibenzylcyclopentadienyl, or 3,5-bis(trimethylsilyl)cyclopentadienyl. In some embodiments, each G' and G" is methylene, dimethylmethylene, dimethylsilyl, such as dimethylmethylene or dimethylsilyl; such as dimethylsilyl. In some embodiments, each X is hydrocarbyl or halogenated, such as methyl, benzyl, fluoro, or chloro, such as methyl or chloro. In some embodiments, M is zirconium. In alternative embodiments, M is hafnium.

[0126] A subset of metallocene compounds (precatalysts) represented by formula (3) that can be used include those represented by formula (3a) having C s or quasi C s symmetry:

[0127]

[0128] wherein:

[0129] M, G', G", and X are as defined for formula (3);

[0130] R e is selected from hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silylhydrocarbyl, or germylhydrocarbyl group;

[0131] each R f and R g is selected from a hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, silylhydrocarbyl, or germylhydrocarbyl group, with the proviso that each R f and R g is selected to allow the compound to be C s symmetric or quasi C s symmetric.

[0132] In some embodiments of formula (3a), each R fand R g is independently a hydrocarbon group or a silyl hydrocarbon group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or trimethylsilyl, such as methyl, isopropyl, tert-butyl, cyclopentyl, pent-3-yl, cyclohexyl, benzyl, or trimethylsilyl, such as methyl, isopropyl, tert-butyl, benzyl, or trimethylsilyl. In some embodiments, R e It is hydrogen, hydrocarbon, or silyl hydrocarbon, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or trimethylsilyl; such as hydrogen, isopropyl, tert-butyl, 2,2-dimethylpentan-3-yl, 2,2-dimethylbutan-3-yl, or trimethylsilyl, such as hydrogen, isopropyl, or trimethylsilyl.

[0133] In some embodiments, the catalyst of formula (3) is:

[0134]

[0135] In some embodiments of Formula 1, 1a, 1b, 2, 3 or 3a, G, G' and G" are selected from R*2C, R*2Si, R*2Ge, R*2CCR*2, R*C═CR*, R*2CSiR*2, R*2SiSiR*2, R*B, R*2C—BR*, R*N, R*P, O, S and Se, wherein each R* is independently selected from hydrogen, C1-C 20 The substituents are alkyl, substituted alkyl, halogenated alkyl, substituted halogenated alkyl, silylalkyl, or germylalkyl, and optionally, two or more adjacent R* may be linked to form a substituted or unsubstituted saturated, partially unsaturated cyclic or polycyclic substituent. In some embodiments, G, G' and G" are selected from R*2C, R*2Si, R*2Ge, R*2CCR*2, R*B, R*N, R*P, O, S, and Se, wherein each R* is independently selected from hydrogen, C1-C 20 and R*2CCR*2, wherein each R* is independently selected from hydrogen, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, C1-C2-containing alkyl, 20 The invention further comprises a hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl, or germylhydrocarbyl substituent, and optionally, two or more adjacent R* may be linked to form a substituted or unsubstituted saturated, partially unsaturated cyclic or polycyclic substituent.

[0136] The catalysts described herein capable of producing syndiotactic polypropylene polymers and syndiotactic propylene-based ethylene-propylene copolymers can also include a compound (a pre-catalyst) having a structure represented by formula (4) having C2 symmetry:

[0137]

[0138] wherein:

[0139] M is zirconium or titanium;

[0140] O is oxygen;

[0141] N is nitrogen;

[0142] R 1 is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group; 1 is a halocarbyl group;

[0143] R 2 is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group; 2 is a hydrocarbyl group having three or more carbon atoms or a silylcarbyl group having three or more carbon atoms;

[0144] R 3 , R 4 , and R 5 are each independently hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl group; 3 , R 4 , and R 5 are hydrogen;

[0145] each X is independently a hydride, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a silylcarbyl, or a germylcarbyl group; or two Xs are joined and bound to the metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms; or two Xs together can be an olefinic, diene, or aryne ligand; two Xs can independently be a halogen, alcoholate, aryloxide, amide, phosphide, or other univalent anionic ligand, or two Xs can also be joined to form a dianionic chelating ligand.

[0146] In some embodiments of formula (4), R 1is a hydrocarbyl or halogenated alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, perfluorophenyl, trifluorophenyl, difluorophenyl, or fluorophenyl, such as phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2- isopropylphenyl, perfluorophenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5- difluorophenyl, or 4-fluorophenyl, such as perfluorophenyl. In some embodiments, R2is a hydrocarbyl or silylhydrocarbyl group, such as C3-C 12 hydrocarbyl or C3-C 12 silylhydrocarbyl, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, cumyl, or trimethylsilyl, such as isopropyl, t-butyl, cumyl, or trimethylsilyl, such as t-butyl or trimethylsilyl. In some embodiments, R 3 , R 4 , and R 5 are independently hydrogen or a hydrocarbyl group. In some embodiments, each X is a hydrocarbyl or halogen, for example, methyl, benzyl, fluoro, or chloro, such as methyl or chloro. In some embodiments, M is titanium.

[0147] In some embodiments, the catalyst compound of formula (4) is:

[0148]

[0149] Activators and catalyst activation

[0150] The terms "cocatalyst" and "activator" are used interchangeably herein and are defined as any compound which can activate any of the aforementioned precatalyst compounds by converting the neutral precatalyst compound to a catalytically active cationic compound. For example, non-limiting activators include aluminoxane, alkylaluminum, ionizing activators (which can be neutral (Lewis acid activators) or ionic (ionic activators)), and cocatalysts of the conventional type. The activator can include an aluminoxane compound, a modified aluminoxane compound, or an ionized anion precursor compound which abstracts a reactive sigma-bound metal ligand, cationizes the metal complex, and provides a charge-balancing non-coordinating or weakly coordinating anion.

[0151] Aluminoxane activators can be used as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds comprising -Al(R 1 )-O- sub-units, wherein R 1is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable for use as catalyst activators, especially when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. A visually clear methylaluminoxane can be used. A clear solution can be obtained by filtering a hazy or gelled aluminoxane, or the clear aluminoxane can be decanted from a hazy solution. One useful aluminoxane is a 3A type modified methylalumoxane (MMAO) co-catalyst (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, protected by U.S. Patent No. 5,041,584). Another useful aluminoxane is a solid polymethylaluminoxane, as described in US 9,340,630, US 8,404,880, and US 8,975,209.

[0152] When the activator is an aluminoxane (modified or unmodified), at least one embodiment selects a maximum use of the activator, typically up to 5000-fold molar excess of Al / M per metal catalytic site of the catalyst compound. The minimum molar ratio of activator to catalyst compound is 1 : 1. Alternative suitable ranges include 1 : 1 to 500: 1, or 1 : 1 to 200: 1, or 1 : 1 to 100: 1, or 1 : 1 to 50: 1.

[0153] In alternative embodiments, little or no aluminoxane is used in the polymerization processes described herein. For example, the aluminoxane is present at 0 mol%, or the aluminoxane is present at a molar ratio of aluminum to transition metal of the catalyst compound of less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1.

[0154] Lewis acid activators include triphenylboron, triperfluorophenylboron, triperfluorophenylaluminum, but do not include the class of activators known as aluminoxanes. Ionic activators include dimethylanilinium tetra(perfluorophenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, dimethylanilinium tetra(perfluorophenyl)aluminate. Lewis acid activators and ionic activators are known as stoichiometric activators because the molar ratio of activator to transition metal compound needed is relatively low compared to aluminoxane activators (which require an excess of activator relative to transition metal compound). (carbenium)tetra(perfluorophenyl)borate, dimethylanilinium tetra(perfluorophenyl)aluminate. Lewis acid activators and ionic activators are known as stoichiometric activators because the molar ratio of activator to transition metal compound needed is relatively low compared to aluminoxane activators (which require an excess of activator relative to transition metal compound).

[0155] Neutral or ionic activators such as tri(n-butyl)ammonium tetrakis(pentafluorophenylborate), trisperfluorophenylboron, trisperfluoronaphthylboron, polyhalogenated heteroborane anions, boric acid, or combinations thereof may also be used.

[0156] Stoichiometric amounts of activator (sometimes used in combination with a co-activator) can be used to produce the syndiotactic polypropylene homopolymers and syndiotactic propylene-based ethylene-propylene copolymers described herein.

[0157] For example, activators that can be used are trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilino tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilino)tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilino tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilino tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, ammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilino tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilino tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilino)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate (wherein the alkyl group is methyl, ethyl, propyl, n-butyl, isobutyl, or tert-butyl).

[0158] In at least one embodiment, the activator is one or more of the following: N,N-dimethylanilino tetrakis (perfluorophenyl) borate, N,N-dimethylanilino tetrakis (perfluoronaphthyl) borate, N,N-dimethylanilino tetrakis (perfluorobiphenyl) borate, N,N-dimethylanilino tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbonyl borate, Tetrakis(perfluoronaphthyl)borate, triphenylcarbon Tetrakis(perfluorobiphenyl)borate, triphenylcarbon Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbon Tetrakis(perfluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-diethylanilinotetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilino)tetrakis(perfluoronaphthyl)borate, Other useful activators include: N-methyl-4-nonadecyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilino[tetra(perfluorophenyl)borate], N-methyl-4-hydrogenated methyl ammonium tetra(perfluorophenyl)borate ... -Methyl-4-octyl-N-octadecylanilino[tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilino[tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilino[tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilino[tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilino[tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylbenzene Amine [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilino [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilino [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecadecylammonium [tetrakis(perfluorophenyl)borate], ammonium[tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium[tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium[tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium[tetrakis(perfluorophenyl)borate], N,N-bis(octadecyl)tolylammonium[tetrakis(perfluorophenyl)borate], N,N-bis(hexadecyl)tolylammonium[tetrakis(perfluorophenyl)borate], N,N-bis(tetradecyl)tolylammonium[tetrakis(perfluorophenyl)borate], N,N-dodecyl-N'-dodecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-octadecyl-N'-hexadecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-octadecyl-N'-hexadecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-octadecyl-N'-tetradecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-octadecyl-N'-dodecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-octadecyl-N'-decyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-hexadecyl-N'-tetradecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-hexadecyl-N'-dodecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-hexadecyl-N'-decyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-tetradecyl-N'-dodecyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-tetradecyl-N'-decyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-dodecyl-N'-decyl-N'-methylphenylammonium [tetrakis(perfluorophenyl) borate], N-methyl-N'-octadecyl anilinium [tetrakis(perfluorophenyl) borate], N-methyl-N'-hexadecyl anilinium [tetrakis(perfluorophenyl) borate], N-methyl-N'-tetradecyl anilinium [tetrakis(perfluorophenyl) borate], N-methyl-N'-dodecyl anilinium [tetrakis(perfluorophenyl) borate], N-methyl-N'-decyl anilinium [tetrakis(perfluorophenyl) borate], and N-methyl-N'-octyl anilinium [tetrakis(perfluorophenyl) borate],

[0159] Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof. The three substituent groups are each independently selected from the group consisting of alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy, and halide. For example, the three substituent groups are independently selected from the group consisting of halogen, mono- or polycyclic (including halogenated) aryl, alkyl, and alkenyl compounds, and mixtures thereof, such as, for example, alkenyl groups having from 1 to 20 carbon atoms, alkyl groups having from 1 to 20 carbon atoms, alkoxy groups having from 1 to 20 carbon atoms, and aryl groups having from 3 to 20 carbon atoms (including substituted aryl groups). In some embodiments, the three substituent groups are alkyl groups having from 1 to 4 carbon atoms, phenyl groups, naphthyl groups, or mixtures thereof. In some embodiments, the three substituent groups are halogenated (e.g., fluorinated) aryl groups. In some embodiments, the neutral stoichiometric activator is tri(perfluorophenyl)boron or tri(perfluoronaphthyl)boron.

[0160] Ionic stoichiometric activator compounds may contain an active proton or some other cation which is associated with but not coordinated or only loosely coordinated to the remaining ion of the ionizing compound. Such compounds are described in the European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299, 5,502,124, 5,972,823, and publications US2021079537, WO2021 / 086467, US2019 / 0330169, and US2019 / 0330392, all of which are incorporated herein by reference.

[0161] Ionic catalysts can be prepared by reacting a transition metal compound with an activator (e.g., B(C6F6)3) which reacts with a hydrolyzable ligand (X') of the transition metal compound to form an anion (e.g., [B(C6F5)3(X')] - ), which can stabilize the cationic transition metal species generated by the reaction. The catalyst can be prepared using an ionic compound or activator component of the composition. However, it is also contemplated to use a neutral compound to prepare the activator.

[0162] The compound used as the activator component in the preparation of the ionic catalyst system used in this process comprises a cation and a compatible non-coordinating anion, wherein the cation may be a Bronsted acid capable of donating a proton ( The anion is relatively large (bulky) and can stabilize the active catalyst species formed when the two compounds combine. The anion is also sufficiently mobile to be displaced by olefinic dienes, acetylenic unsaturated species, or other neutral Lewis bases (e.g., ethers, nitriles, etc.). EPA 277,003 and EPA 277,004 (published in 1988) disclose two types of compatible non-coordinating anions: 1) anionic coordination complexes containing multiple lipophilic groups covalently coordinated to and shielding a central charged metal or metalloid core; and 2) anions containing multiple boron atoms, such as carboranes, metallocarboranes, and boranes.

[0163] In at least one embodiment, the ionic stoichiometry of the activator comprises a cationic component and an anionic component and can be represented by the formula:

[0164] (L**-H) d + (A d- )

[0165] in:

[0166] L** is a neutral Lewis base; H is hydrogen; (L**-H)+ is a Bronsted acid; A d- It is a non-coordinating anion having a charge d-, where d is an integer from 1 to 3.

[0167] Cationic component ((L**-H) d +) may include a Bronsted acid, such as a proton or protonated Lewis base, or a reducible Lewis acid, which is capable of protonating a group (such as an alkyl or aryl group) of the alkylated precatalyst or abstracting a group (such as an alkyl or aryl group) from the alkylated precatalyst.

[0168] Activated cation (L**-H) d + can be a Bronsted acid that can donate a proton to the alkylated transition metal catalytic precursor to generate a transition metal cation, including ammonium, oxygen 、 , silylium, and mixtures thereof, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, ammonium from triethylphosphine, triphenylphosphine and diphenylphosphine , from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and di Oxygen of alkane , sulfonium from sulfides such as diethyl sulfide and tetrahydrothiophene, and mixtures thereof. Activated cations (L**-H) d + can also be silver, (tropylium), carbenium, ferrocenium, and mixtures thereof, such as carbenium and ferrocenium; such as triphenylcarbenium . Anionic component A d- Including having the formula [M k+ Q n ] d-wherein k is an integer from 1 to 3; n is an integer from 2 to 6; n - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, such as boron or aluminum, and Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halogenated hydrocarbyl, a substituted halogenated hydrocarbyl, and a halogen-substituted-hydrocarbyl radical, said Q having up to 20 carbon atoms, with the proviso that Q is not a halide more than once. For example, each Q is a fluoro hydrocarbyl radical having from 1 to 20 carbon atoms, such as each Q is a fluoro aryl radical, such as each Q is a pentafluoro aryl radical. Suitable A d- Examples also include the diboron compounds disclosed in U.S. Patent No. 5,447,895, which is incorporated by reference herein in its entirety.

[0169] In some embodiments, in making the catalysts of the present disclosure, the boron compound that can be used as a non-coordinating anion activator in combination with a co-activator is a tri-substituted ammonium salt, for example: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetra(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate, N,N-diethylanilinium tetra(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetra(pentafluorophenyl)borate, trimethylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetra-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetra-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetra-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetra-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetra-(2,3,4,6-tetrafluorophenyl)borate, trimethylammonium tetra(perfluoronaphthyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetra(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetra(perfluoronaphthyl)borate, N,N-dimethylanilinium tetra(perfluoronaphthyl)borate, N,N-diethylanilinium tetra(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetra(perfluoronaphthyl)borate, trimethylammonium tetra(perfluorobiphenyl)borate, triethylammonium tetra(perfluorobiphenyl)borate, tripropylammonium tetra(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetra(perfluorobiphenyl)borate, tri(t-butyl)ammonium tetra(perfluorobiphenyl)borate, N,N-dimethylanilinium tetra(perfluorobiphenyl)borate, N,N-diethylanilinium tetra(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetra(perfluorobiphenyl)borate, trimethylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetra(3,5-bis(trifluoromethyl)phenyl)borate, and the like.5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkylammonium salts such as di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetrakis(pentafluorophenyl)borate; and other salts such as tris(ortho-tolyl)phosphite, tetrakis(pentafluorophenyl)borate, tris(2,6-dimethylphenyl)phosphite tetrakis(pentafluorophenyl)borate, (tropillium) tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenyl tetraphenylborate, triethylsilyl tetraphenylborate, diazonium tetraphenylborate, tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, triphenyl tetrakis(pentafluorophenyl)borate, triethylsilyl tetrakis(pentafluorophenyl)borate, diazonium tetrakis(pentafluorophenyl)borate, tetra-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetra-(2,3,4,6-tetrafluorophenyl)borate, triphenyl tetra-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyl tetra-(2,3,4,6-tetrafluorophenyl)borate, diazonium tetra-(2,3,4,6-tetrafluorophenyl)borate, tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenyl tetrakis(perfluoronaphthyl)borate, triethylsilyl tetrakis(perfluoronaphthyl)borate, diazonium tetrakis(perfluoronaphthyl)borate, tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenyl tetrakis(perfluorobiphenyl)borate, triethylsilyl tetrakis(perfluorobiphenyl)borate, diazonium tetrakis(perfluorobiphenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenyl tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyl tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and diazonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0170] In some embodiments, the non-coordinating anion activator (L**-H) d + (A d- ) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N- dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetrakis(perfluorophenyl)borate.

[0171] The catalyst precursor can also be activated with a co-catalyst or activator that includes a non-coordinating anion that does not contain a metallocycle ring anion, as described in U.S. Patent Publication 2002 / 0058765 Al, which is incorporated herein by reference. The addition of a co-activator is required in the catalyst precursors for the present disclosure. A "compatible" non-coordinating anion is one that does not degrade upon dissociation from the initially formed complex to a neutral anion. In addition, the anion does not transfer an anionic substituent or fragment to the cation, resulting in the formation of a neutral transition metal compound and a neutral byproduct of the anion. Exemplary non-coordinating anions for use in accordance with the present disclosure are those that are compatible, stabilize the transition metal complex cation in the sense of balancing its ionic charge +1, and still retain sufficient liability to allow displacement by an olefinically or acetylenically unsaturated monomer during polymerization. These types of co-catalysts are sometimes used with a scavenger, such as, but not limited to, triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, triethylaluminum, or trimethylaluminum.

[0172] The disclosed process can also employ a co-catalyst compound or activator compound that is initially a neutral Lewis acid, but forms a cationic metal complex and a non-coordinating anion, or a zwitterionic complex upon reaction with an alkylated transition metal compound. The alkylated metallocene compound is formed from the reaction of a catalyst precursor and a co-activator. For example, tris(pentafluorophenyl)boron or aluminum acts to abstract a hydrocarbyl ligand, generating the disclosed cationic transition metal complex and a stable non-coordinating anion, see EP-A-0 427 697 and EP-A-0 520 732 for similar Group 4 metallocene compounds. Also, see the processes and compounds in EP-A-0495 375. For the use of similar Group 4 compounds to form zwitterionic complexes, see U.S. Patent Nos. 5,624,878; 5,486,632; and 5,527,929.

[0173] Other neutral Lewis acids known in the art are also suitable for abstracting formally anionic ligands. See, for example, the review article by E. Y.-X. Chen and T. J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).

[0174] When the cation of the non-coordinating anion activator is a Bronsted acid such as a proton or a protonated Lewis base (excluding water), or a reducible Lewis acid such as ferrocene or a silver cation, or an alkali or alkaline earth metal cation, such as sodium, magnesium, or lithium cation, the molar ratio of catalyst-precursor to activator can be any ratio. Combinations of the activator compounds described can also be used for activation.

[0175] When an ionic or neutral stoichiometric activator (such as an NCA) is used, the molar ratio of catalyst-precursor to activator is 1 : 10 to 1 : 1, 1 : 10 to 10: 1, 1 : 10 to 2: 1, 1 : 10 to 3: 1, 1 : 10 to 5: 1, 1 : 2 to 1.2: 1, 1 : 2 to 10: 1, 1 : 2 to 2: 1, 1 : 2 to 3: 1, 1 : 2 to 5: 1, 1 : 3 to 1.2: 1, 1 : 3 to 10: 1, 1 : 3 to 2: 1, 1 : 3 to 3: 1, 1 : 3 to 5: 1, 1 : 5 to 1 : 1, 1 : 5 to 10: 1, 1 : 5 to 2: 1, 1 : 5 to 3: 1, 1 : 5 to 5: 1, 1 : 1 to 1 : 1.2. The molar ratio of catalyst-precursor to co-activator is 1 : 500 to 1 : 1, 1 : 100 to 100: 1, 1 : 75 to 75: 1, 1 : 50 to 50: 1, 1 : 25 to 25: 1, 1 : 15 to 15: 1, 1 : 10 to 10: 1, 1 : 5 to 5: 1, 1 : 2 to 2: 1, 1 : 100 to 1 : 1, 1 : 75 to 1 : 1, 1 : 50 to 1 : 1, 1 : 25 to 1 : 1, 1 : 15 to 1 : 1, 1 : 10 to 1 : 1, 1 : 5 to 1 : 1, 1 : 2 to 1 : 1, 1 : 10 to 2: 1.

[0176] In some embodiments, the activator and activator / co-activator combinations include dimethylaminotetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron, or a mixture of trialkylaluminum and dimethylaminotetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron. In some embodiments, a scavenger compound is used with the activator. Typical aluminum or borane based components used as scavengers are of the general formula R x J'Z'2, where J' is aluminum or boron, and Rx As defined above, each Z' is independently R x or a different monovalent anionic ligand such as halogen (CI, Br, I), alkoxy (OR x ), and the like. The aluminum alkyls can include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, trimethylaluminum, and the like. The boron alkyls can include triethylboron. The scavenger compounds can be aluminoxanes and modified aluminoxanes, including methylaluminoxane and modified methylaluminoxane.

[0177] In some embodiments, the pre-catalyst and or activator are combined with an aluminum alkyl compound, such as a trialkylaluminum compound, prior to entering the reactor. For example, the aluminum alkyl compound can be represented by the formula R3Al, where each R is independently a Ci to C 20 alkyl group; for example, the R groups are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isooctyl, n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl, n-decyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl, such as isobutyl, n-octyl, n-hexyl, and n-dodecyl. In some embodiments, the aluminum alkyl compound is selected from the group consisting of triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, and tri-n-dodecylaluminum.

[0178] Chain transfer agents

[0179] The polymerization process of the present disclosure can include polymerization in the presence of a chain transfer or chain shuttling agent.

[0180] The chain transfer agent includes an aluminum alkyl compound represented by the formula: R3Al, where each R is independently a Ci to C 18 alkyl group; for example, the R groups are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isooctyl, n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl, n-decyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl, such as isobutyl, n-octyl, n-hexyl, and n-dodecyl. In some embodiments, the aluminum alkyl compound is selected from the group consisting of triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, and tri-n-dodecylaluminum.

[0181] In this process, hydrogen can also be used as a chain transfer agent useful in the reaction. In some embodiments, alternative chain transfer agents can be used in the processes described herein, thereby reducing the need for hydrogen or using limited amounts of hydrogen. In some embodiments, the chain transfer agent includes diethyl zinc and a trialkylaluminum, such as triisobutylaluminum, tri-n-octylaluminum, triethylaluminum, and the like, or mixtures thereof.

[0182] In some embodiments, the chain transfer agent can be used in a molar ratio of chain transfer agent to transition metal compound of 1 : 1 to 150: 1. In at least one embodiment, the molar ratio of chain transfer agent to transition metal compound can be greater than 5: 1, or greater than 10: 1, or greater than 20. Likewise, the molar ratio of chain transfer agent to transition metal compound can be less than 120: 1, or less than 100: 1, or less than 80: 1.

[0183] Polymerization process

[0184] Ethylene-propylene copolymers based on syndiotactic propylene can be produced by contacting ethylene and propylene with at least one catalyst in any manner known in the art. Any homogeneous, bulk, solution (including supercritical), slurry-phase, and gas phase polymerization processes known in the art can be used. These processes can be operated in batch, semi-batch, or continuous mode. These processes can also be operated in systems having a single reactor or multiple reactors in series and / or parallel configuration. Homogeneous polymerization processes are preferred. A homogeneous polymerization process is defined as a process in which at least 90 wt% of the product is soluble in the reaction medium under polymerization conditions. The monomers themselves can also be used as the solvent / diluent in a bulk polymerization process. A bulk process generally refers to a process in which the monomer concentration in all feeds to the reactor is 70 vol% or more. Alternatively, no solvent or diluent is present in, or added to, the reaction medium (except for small amounts used as a carrier for the catalyst system or other additives, or amounts normally present with the monomers, such as propane in propylene).

[0185] Suitable diluents / solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; n-alkanes (such as Norpar solvents from ExxonMobil Chemical Company, Houston, Texas), or isoparaffinic solvents (such as Isopar solvents from ExxonMobil Chemical Company, Houston, Texas) (Isopar TM ); cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and alkyl-substituted aromatic compounds, such as toluene, and or xylene, and or ethylbenzene; perhalogenated hydrocarbons, such as perfluorinated C 4-10Alkanes, chlorobenzene. Mixtures of any of the above hydrocarbon solvents can also be used. Suitable solvents also include liquid olefins which can be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, the solvent used is an aliphatic hydrocarbon solvent such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not an aromatic compound, preferably, the solvent contains less than 1 wt.%, preferably less than 0.5 wt.%, preferably less than 0 wt.% aromatic compounds, based on the weight of the solvent.

[0186] The preferred polymerization can be conducted at any temperature and / or pressure suitable to obtain the desired polymer. Typical temperatures and / or pressures include temperatures ranging from about 50°C to about 200°C, from about 55°C to about 150°C, from about 58°C to about 120°C, preferably from about 60°C to about 110°C, preferably from about 60°C to about 90°C; and pressures ranging from about 0.35 MPa to about 14 MPa, preferably from about 2 MPa to about 13 MPa, preferably from about 4 MPa to about 13 MPa, preferably from about 7 MPa to about 12 MPa, preferably from about 9 MPa to about 11.5 MPa, preferably from about 9 MPa to about 11 MPa. In some catalyst systems, the syndiotacticity of the ethylene-propylene copolymer varies with the polymerization temperature, and the temperature can be selected to achieve a desired level of syndiotacticity in the ethylene-propylene copolymer. In one embodiment, the polymerization is conducted at a temperature of 60°C or higher, with an upper temperature limit of 120°C, and a pressure of 9.5 MPa or higher.

[0187] In one embodiment, the polymerization is conducted at a polymerization temperature of TP1 or higher, where TP1 = 0.9*EXP(-0.005*rr). Preferably, the polymerization temperature is at least TP2, where TP2 = 1.15*EXP(-0.006*rr). The units of TP1 and TP2 are °C, and rr is the syndiotacticity of the ethylene-propylene copolymer as measured using 13 C NMR measured triad tacticity index of the syndiotactic ethylene-propylene copolymer.

[0188] In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa). In some embodiments, hydrogen is not added to the polymerization reactor, i.e., hydrogen can come from other sources, such as a hydrogen generation catalyst, but is not added to the reactor. Alternatively, the hydrogen concentration in the feed is 10,000 ppm or less, preferably 5,000 ppm or less.

[0189] When the polymerization is carried out in a continuous process, the catalyst generally has a catalyst activity greater than 10,000 kg of polymer per kg of catalyst or more, 20,000 kg of polymer per kg of catalyst or more, 50,000 kg of polymer per kg of catalyst or more, or 100,000 kg of polymer per kg of catalyst or more. Likewise, the conversion of the olefin monomer is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, or preferably 80% or more, based on the polymer yield and the weight of monomer entering the reaction zone.

[0190] The catalyst and activator can be delivered as a solution, pure liquid, suspension, or slurry. They can be delivered to the reactor separately and activated in-line before entering the reactor, or they can be preactivated and pumped to the reactor as an activated solution or slurry. In one embodiment, the catalyst and activator can be fed to the polymerization reactor as a dry powder or slurry without the need to prepare a homogeneous catalyst solution by dissolving the catalyst in a carrier solvent.

[0191] The ethylene-propylene copolymers based on syndiotactic propylene can also include at least one other monomer and can be prepared by contacting ethylene, propylene, and at least one other monomer with at least one catalyst in any manner known in the art. Suitable other monomers include substituted or unsubstituted C2to C40alpha olefins, preferably C2to C20alpha olefins, preferably C2to C12alpha olefins, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In preferred embodiments of the present application, the monomers include propylene and optionally a comonomer, the comonomer including ethylene or one or more of C4to C40olefins, preferably C4to C20olefins, or preferably C6to C12olefins. The C4to C40olefin monomers can be linear, branched, or cyclic. The C4to C40cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and can optionally include heteroatoms and / or one or more functional groups. Exemplary C2to C40olefin monomers and optional comonomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and respective homologues and derivatives thereof, preferably norbornene, norbornadiene, and dicyclopentadiene. Preferably, the polymer is a syndiotactic-rich ethylene-propylene-hexene terpolymer or a syndiotactic-rich ethylene-propylene-octene terpolymer.

[0192] The polymerization reaction can be carried out in multiple reactors configured in series or in parallel. In one embodiment, the copolymer is a reactor blend of the first polymer component and the second polymer component. Thus, the comonomer content of the copolymer can be adjusted by adjusting the comonomer content of the first polymer component, adjusting the comonomer content of the second polymer component, and / or adjusting the ratio of the first polymer component to the second polymer component in the copolymer.

[0193] The ethylene-propylene copolymers based on syndiotactic propylene according to the various embodiments can be a blend of at least two ethylene-propylene copolymers based on syndiotactic propylene. The blend can be made using two or more reactors in series or in parallel. Preferably, the blend has a bimodal or broad molecular weight distribution (MWD > 3.0). The blend can also have a bimodal or broad composition distribution. Preferably, one component has an ethylene content ranging from 0.2 to 5 wt% and one component has an ethylene content ranging from 2 to 15 wt%. When multiple reactors are used, each blend component can be made in a different reactor. This can be achieved by operating the reactors at different polymerization conditions and / or using different catalysts in each reactor. The ethylene-propylene copolymer blend based on syndiotactic propylene can also be made in a single reactor using multiple catalysts. In one embodiment, one component has a Mw of 10,000 to 30,000 g / mol, an ethylene content of 0.2 wt% to 3 wt%, and one component has a Mw of 30,000 to 200,000 g / mol, an ethylene content of 2 wt% to 10 wt%.

[0194] In one embodiment, a solution polymerization process is preferred. Solution polymerization processes can be used to carry out the polymerization reactions disclosed herein in any suitable manner known to one of ordinary skill in the art. In a particular embodiment, the polymerization process can be carried out in a continuous polymerization process. The term "batch" refers to a process in which the entire reaction mixture is withdrawn from the polymerization reactor vessel at the end of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are continuously introduced to the reactor vessel and a solution containing the polymer product is simultaneously or nearly simultaneously withdrawn. Solution polymerization refers to a polymerization process in which the resulting polymer is soluble in the liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerization is generally homogeneous. Preferably, such a system is not hazy, as described by J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res. 29, 2000, 4627.

[0195] In a typical solution process, catalyst components, solvent, monomers, and hydrogen (when used) are fed to one or more reactors under pressure. Temperature control in the reactor is generally achieved by balancing the heat of polymerization, cooling the contents of the reactor with cooling coils or by a reactor jacket, auto refrigeration, reactor cooling of pre-cooled feeds, vaporization of a liquid medium (diluent, monomer, or solvent), or a combination of the three. An insulated reactor with pre-cooled feeds can also be used. The monomers are dissolved / dispersed in the solvent prior to entering the first reactor, or dissolved in the reaction mixture. The solvent and monomers are generally purified to remove potential catalyst poisons prior to entering the reactor. The feedstock can be heated or cooled prior to being fed to the first reactor. Additional monomers and solvent can be added to the second reactor and heated or cooled. The catalyst / activator can be fed to the first reactor or split between the two reactors. During solution polymerization, the polymer produced is molten under reactor conditions and remains dissolved in the solvent, forming a polymer solution (also referred to as effluent).

[0196] The solution polymerization process of the present invention uses an agitated tank reactor system comprising one or more agitated polymerization reactors. Generally, the reactors should be operated under conditions that allow for sufficient mixing of the reactants. In a multiple reactor system, the first polymerization reactor is preferably operated at a lower temperature. The residence time in each reactor depends on the design and capacity of the reactor. The catalyst / activator can be fed to the first reactor only or split between the two reactors. In an optional embodiment, the present invention can employ a loop reactor and a plug flow reactor.

[0197] The polymer solution is then discharged from the reactor as an effluent stream, and the polymerization reaction is quenched, typically using a coordinating polar compound, to prevent further polymerization. After leaving the reactor system, the polymer solution is passed through an in-line heat exchanger system, into a devolatilization system and polymer finishing processes. The phase separation and volatiles removed downstream can be recycled and become part of the polymerization feed.

[0198] The polymer is recovered from the effluent of either reactor or the combined effluents by separating the polymer from the other components of the effluent. Conventional separation means can be employed. For example, the polymer can be recovered from the effluent by coagulation with a non-solvent (such as isopropyl alcohol, acetone, or n-butanol, etc.), or by heating and vacuum stripping of the solvent or other medium using heat and steam. During recovery, one or more conventional additives, such as antioxidants, can be added to the polymer. Other recovery methods are also contemplated, such as by using a lower critical solution temperature (LCST) followed by devolatilization.

[0199] In one embodiment, the polymerization: 1) is conducted in a solution process at a temperature of 50°C or greater (preferably 60°C or greater, preferably 65°C or greater) with an upper temperature limit of 120°C or less, or 110°C or less, or 100°C or less; 2) is conducted at a pressure of from atmospheric pressure to 15 MPa (preferably 1 to 15 MPa, preferably 2 to 14 MPa, preferably 4 to 13 MPa); 3) is conducted in a solvent that is: an aliphatic hydrocarbon solvent such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; a cyclic and alicyclic hydrocarbon such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably, wherein aromatic compounds (such as toluene) are present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based on the weight of the solvent; 4) ethylene is present in the polymerization reactor at a concentration of 2 moles / liter or less; 5) the polymerization reaction is preferably conducted in one reaction zone; 6) the catalyst compound has a productivity of 5,000 kg of polymer per kg of catalyst or more (preferably 10,000 kg of polymer per kg of catalyst or more, such as 20,000 kg of polymer per kg of catalyst or more, such as 40,000 kg of polymer per kg of catalyst or more, such as 50,000 kg of polymer per kg of catalyst or more, such as the catalyst efficiency can be from about 10,000 kg of polymer per kg of catalyst to about 500,000 kg of polymer per kg of catalyst).

[0200] The composition of the ethylene-propylene copolymer based on syndiotactic propylene according to the different embodiments varies with the feed composition and the concentration of the monomers in the polymerization reactor. In one embodiment, the molar ratio of ethylene to propylene in the feed is 0.29 or less, preferably 0.25 or less, preferably 0.20 or less, preferably 0.15 or less, preferably 0.10 or less. In another embodiment, the molar ratio of ethylene to propylene in the feed is 0.03 or more, preferably 0.035 or more.

[0201] In a preferred embodiment, the polymerization is conducted in a solution process at a pressure of 9 MPa or greater, at a temperature of 60°C or greater with an upper temperature limit of 120°C, and the catalyst efficiency is from 50,000 kg of polymer per kg of catalyst to about 600,000 kg of polymer per kg of catalyst.

[0202] Preferably, the polymerization is conducted in a solution process at a pressure of 9 MPa or greater, the molar ratio of ethylene to propylene in the feed is 0.03 or more, and the catalyst efficiency is from 50,000 kg of polymer per kg of catalyst to about 600,000 kg of polymer per kg of catalyst.

[0203] Gel permeation chromatography with three detectors (GPC-3D)

[0204] Molecular weights (number average molecular weight (Mn), weight average molecular weight (Mw) and z average molecular weight (Mz)) were determined using an Agilent PL220 high temperature GPC (gel permeation chromatograph) equipped with an online differential refractive index (DRI) detector, a light scattering (LS) detector and a viscometer (VIS) detector. Separation was performed using three Polymer Laboratories PLgel 10 μm Mixed-B columns with a nominal flow rate of 0.5 ml / min and a nominal injection volume of 300 microliters. The detectors and columns were placed in an oven maintained at 145°C. Details of these detectors and their calibration are described, for example, by T. Sun, P. Brant, RR Chance and WW Graessley in Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001), which is incorporated herein by reference.

[0205] The solvent for GPC testing was prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 micron Teflon filter. The TCB was then degassed using an online degasser before entering the GPC. The polymer solution was prepared by placing the dry polymer in a glass container, adding the required amount of TCB, and then heating the mixture at 160°C with continuous stirring for approximately 2 hours. All quantities were measured gravimetrically. The injection concentration was 1.0 to 2.0 mg / mL, with lower concentrations used for samples with higher molecular weight. The concentration c of each point in the chromatogram was calculated from the baseline-subtracted DRI signal I DRI Calculate using the following equation:

[0206] c=K DRI I DRI / (dn / dc)

[0207] Among them, K DRI is a constant determined by calibrating the DRI with a series of monodisperse polystyrene standards with molecular weights ranging from about 600 to 11 M; (dn / dc) is the refractive index increment of the system. For the purposes of this invention and the claims thereto, for all ethylene-propylene copolymers and homopolymers, (dn / dc) = 0.1048. The units used in this GPC method description are: concentration in g / cm 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity is expressed in dL / g.

[0208] The light scattering detector was a high temperature 18-angle Dawn Heleos (Wyatt Technology, Inc.) The molecular weight, M, of each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):

[0209]

[0210] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by DRI analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o is the optical constant of the system:

[0211]

[0212] where N A is the Avogadro number and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ=690nm is n=1.500. The specific viscosity is determined using a high-temperature Agilent viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector and the other sensor, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is s The intrinsic viscosity [η] at each point in the chromatogram is calculated from their outputs by the following equation:

[0213] η s =c[η]+0.3(c[η]) 2

[0214] Where c is the concentration, determined by the DRI output.

[0215] g' 粘度 It is defined as the ratio of the intrinsic viscosity of a syndiotactic ethylene-propylene copolymer to the intrinsic viscosity of an isotactic-rich propylene-ethylene copolymer of equal molecular weight and composition and is calculated as follows using the output of the SEC-DRI-LS-VIS method. The average intrinsic viscosity of the sample [η] 平均 By the following calculation:

[0216]

[0217] where the sum is over all chromatographic slices i between the integration limits.

[0218] g' 粘度 defined as:

[0219]

[0220] M v viscosity average molecular weight based on LS analysis, while a and K are calculated according to published literature (T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001)), but for the purposes of the present invention and claims thereto, a = 0.695 + TRUNC(10*C3wt) / 1000 and K = 0.000579*(1-0.48601*C3wt-0.068989*C3wt^2)*(200000)^(-TRUNC(10*C3wt) / 1000) for ethylene-propylene copolymers. C3wt is the propylene content of the copolymer in weight percent, concentration in g / cm 3 g / mole, intrinsic viscosity (i.e., K in the Mark-Houwink equation) in dL / g, unless otherwise specified.

[0221] Differential scanning calorimetry (DSC)

[0222] Peak melting point Tm(also referred to as melting point), peak crystallization temperature Tc(also referred to as crystallization temperature), glass transition temperature Tg, heat of fusion (ΔHf or Hf), and percent crystallinity were determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetry (DSC) data were obtained using a TA Instruments model Q200 instrument. Samples of about 5-10 mg were sealed in aluminum hermetic sample pans. The samples were first gradually heated at a rate of 10 °C / min to 200 °C and the DSC data were recorded. The sample was held at 200 °C for 2 min, then cooled at a rate of 10 °C / min to -90 °C, followed by an isothermal of 2 min, and then heated at a rate of 10 °C / min to 200 °C. The thermal events of the first and second cycles were recorded. The area under the endothermic peak was measured to determine the heat of fusion and percent crystallinity. The formula for percent crystallinity is [area under melting peak (J / g) / B (J / g)]*100, where B is the heat of fusion for a 100% crystalline homopolymer of the major monomer component. These B values can be obtained from the Polymer Handbook (Fourth Edition) published by John Wiley and Sons (New York 1999), but a value of 189 J / g (B) was used for the heat of fusion for a 100% crystalline polypropylene and a value of 290 J / g was used for the heat of fusion for a 100% crystalline polyethylene. The melting and crystallization temperatures reported here were obtained in the second heating / cooling cycle unless otherwise stated.

[0223] Carbon NMR

[0224] The comonomer content and sequence distribution of polymers can be determined using 13 C nuclear magnetic resonance (NMR) was measured by methods well known to those skilled in the art. Unless otherwise stated, the polymer samples for C NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2at a concentration of 67 mg / mL at 140 °C and recorded using a Bruker NMR spectrometer at 120 °C, 13 C NMR spectroscopy was performed on a Bruker Avance III 400 MHz spectrometer equipped with a 5 mm BBI probehead. The samples were prepared by dissolving 50-100 mg of polymer in 1 mL of 1,1,2,2-tetrachloroethane-d2at 140 °C. The samples were recorded at 120 °C using a 10 mm broad band inverse detection probehead. The samples were spun at 10 kHz and the data were collected using a 4 mm dual axis pulsed field gradient H-C unit operating at 100 kHz. The data were collected using a 90° pulse width, 4.0 s relaxation delay, 2.0 s acquisition time, 4.0 s pulse repetition delay, 32 transients, and 2.0 s recycle delay. The data were processed using Topspin 3.0 software. The chemical shifts were referenced to the methyl protons of the solvent at 5.24 ppm. The data were analyzed using the Bruker software package. 13CNMR frequencies of 125 MHz or higher using a 10 mm cryoprobe with 90° pulses and gated decoupling with at least 512 scans. The chemical shift reference value for the solvent, 1,1,2,2-tetrachloroethane-d2, is 74.24 ppm, so the major isotactic peak for methyl groups is 21.83 ppm. The calculations involved in the characterization of the polymers by NMR follow the work of Bovey, F. A. (1969) in Polymer Conformation and Configuration, Academic Press, New York and Randall, J. (1977) in Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press, New York.

[0225]

[0226] The linest function in excel was used to solve the system of equations assuming the constants were zero and the output was the triad area. Y was defined as the area of the chemical shift region and X was the triad contribution for each region. Then, the individual areas could be divided by the total area to convert them to the mole fraction of the triad, for example, PPP (area) from linest / (PPP + PPE + EPE + PEP + EEP + EEE).

[0227] The %rr(PP+EP) was calculated using the CH3 region of propylene as follows.

[0228] Distribution Chemical shift (ppm) Calculation % mm (PP + EP) 21.2-22.3 mm * 100 / total % mr (PP + EP) 20.4-21.2 mr * 100 / total % rr (PP + EP) 19.6-20.4 rr * 100 / total Total mm + mr + rr

[0229] The chemical shift assignments for ethylene-propylene copolymers are described in Randall, “A Review Of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers”, Polymer Reviews, 29:2, 201-5317 (1989). The composition, mole and weight %, triad sequencing, and dyad calculations for the copolymers were also calculated and described following the methods determined by Randall in this paper.

[0230] Unless otherwise stated, the ethylene content of ethylene-propylene copolymers was determined using FTIR according to ASTM D3900. The composition of other polymers can be determined using 13C NMR was obtained by methods well known to those skilled in the art. For the purposes of the claims herein, ethylene content was determined using FTIR.

[0231] Melt flow rate (MFR) was measured according to ASTM D1238-13 at 230 °C and a load of 2.16 kg. High load melt flow rate (MFR HL) was measured according to ASTM D1238 at 230 °C and a load of 21.6 kg.

[0232] Lubricating oil composition

[0233] The ethylene-propylene copolymers based on syndiotactic propylene disclosed herein can be used as additives in lubricating oils. The concentration of the copolymer in the lubricating oil composition ranges from 0.01 wt% to 20 wt% (e.g., 0.5 wt% to 10 wt%, 0.1 to 5 wt%, 3 wt% to 15 wt%, 4 wt% to 12 wt%, 5 wt% to 9 wt%, etc.) based on the total weight of the lubricating oil composition.

[0234] The oil of the lubricating oil (sometimes referred to as the "base stock" or "base oil") is the primary liquid component of the lubricating oil into which additives and other possible oils are blended, for example, to produce the final lubricating oil (or lubricating oil composition). The base oil, which can be used both to make a concentrate and to make a lubricating oil composition therefrom, can be selected from natural (vegetable, animal, or mineral) and synthetic lubricating oils and mixtures thereof.

[0235] The definitions of base stocks and base oils in this disclosure are the same as those in the American Petroleum Institute (API) Publication 1509 Annex E ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016). Group I base stocks contain less than 90% saturated hydrocarbons and / or greater than 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120, using the test methods specified in API Publication 1509 Annex E. Group II base stocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120, using the test methods specified in API Publication 1509 Annex E. Group III base stocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120, using the test methods specified in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Groups I, II, III or IV.

[0236] Natural oils include animal oils, vegetable oils (such as castor oil and lard) and mineral oils. Animal oils and vegetable oils with good thermal oxidation stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary greatly due to their crude oil sources, for example, they are paraffinic, cycloparaffinic or mixed paraffin-cycloparaffinic. The oil derived from coal or shale is also useful. Natural oils also differ from each other due to their production and purification methods, for example, their distillation ranges, and they are straight run or cracked, hydrorefined, or solvent extracted.

[0237] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized olefins and interpolymerized olefins (such as polybutene, polypropylene, propylene-isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha olefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. For example, PAO derived from C8 to C 14 Olefins (such as C8, C 10 、C 12 、C 14 olefins, or mixtures thereof).

[0238] Other useful fluids for use as base oils include unconventional or unusual base stocks that have been processed, preferably catalytically processed, or synthesized to provide high performance properties.

[0239] Unconventional or non-conventional base stocks include one or more admixtures of base stocks derived from one or more gas to liquid (GTL) materials, and isodewaxate base stocks derived from natural waxes or waxy feedstocks, mineral and or non-mineral oil waxy feedstocks (such as pine waxes), natural waxes, and waxy oil stocks (such as gas oils, waxy fuel hydrocracker residues, waxy residuum fluids, hydrocracking products, thermally cracked materials), or other mineral, mineral oil, or even non-petroleum derived waxy materials (such as waxy materials obtained from coal liquefaction or shale oil).

[0240] The base oil used in the lubricating oil composition of the present disclosure is any of the various oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, more preferably Group III to Group V base oils, as they have excellent volatility, stability, viscosity, and cleanliness properties.

[0241] Generally, the base oil has a kinematic viscosity at 100°C (ASTM D445) in the range of 1.4 to 20 mm 2 / s (e.g., 3 to 12 mm 2 / s, 4 to 10 mm 2 / s, or 4.5 to 8 mm 2 / s).

[0242] The present lubricating oil composition can also include conventional lubricating oil additives for imparting ancillary functions to result in a finished lubricating oil composition having these additives dispersed or dissolved. For example, the lubricating oil composition can be blended with an antioxidant, a dispersant (such as a ashless dispersant), an anti-wear agent, a detergent (such as a metal detergent), a rust inhibitor, a dehazing agent, a demulsifier or de-emulsifier, a friction modifier, a metal deactivator, a pour point depressant, a viscosity modifier, an anti-foam or defoamer, a co-solvent, a package compatibilizer, a corrosion inhibitor, a dye, an extreme pressure agent, and the like, and mixtures thereof. A variety of these additives are known and commercially available. These additives, or their analogs, can be used to make the lubricating oil composition of the present disclosure by conventional blending procedures.

[0243] Each of the foregoing additives is used in a functionally effective amount to impart the desired properties to the lubricant when used. Thus, for example, if the additive is an ashless dispersant, a functionally effective amount of such ashless dispersant is an amount sufficient to impart the desired dispersancy properties to the lubricant. Generally, the concentration of each of these additives, when used, ranges from about 0.001 wt % to about 20 wt %, such as from about 0.01 wt % to about 10 wt %, from about 0.1 wt % to about 5 wt %, and from about 1 wt % to about 4 wt %, unless otherwise specified.

[0244] It is desirable to store and transport the ethylene-propylene copolymers of the present disclosure based on syndiotactic propylene as a concentrate. In a concentrate, the copolymer is typically mixed with a diluent oil for further blending with other lubricating oil additives in the preparation of a fully formulated lubricating oil. The diluent oil can include a Group I, Group II, Group III, Group IV, or Group V oil, or a blend of the foregoing. The diluent oil can also include a Group I oil and a blend of one or more of Group II, Group III, Group IV, or Group V. In some embodiments, the concentrate can include from 0.5 wt % to 50 wt % of the ethylene-propylene copolymer based on syndiotactic propylene.

[0245] The lubricating oil comprising the copolymer composition has a kinematic viscosity at 100°C of at least 2 mm 2 / s (e.g., at least 3 mm 2 / s, at least 4 mm 2 / s, at least 6 mm 2 / s, at least 8 mm 2 / s, at least 10 mm 2 / s, at least 12 mm 2 / s, or at least 15 mm 2 / s). Likewise, the lubricating oil comprising the copolymer composition has a kinematic viscosity at 100°C of 200 mm 2 / s or less (e.g., 150 mm 2 / s or less, 100 mm 2 / s or less, 50 mm 2 / s or less, 40 mm 2 / s or less, 30 mm 2 / s or less, or even 20 mm 2 / s or less).

[0246] The following further embodiments are contemplated to be within the scope of the present disclosure.

[0247] Embodiment AA lubricating oil composition comprising: a major amount of a lubricant base oil; and a minor amount of a viscosity index improver comprising an ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 wt% to 20 wt% ethylene; b) 80 wt% to 98 wt% propylene; c) 50% to 99% rr triads; and d) Mw(LS) of 10 kg / mol to 250 kg / mol.

[0248] Embodiment B The lubricating oil composition of embodiment A, wherein the copolymer has 4 wt% to 18 wt% ethylene.

[0249] Embodiment C The lubricating oil composition of embodiment A, wherein the copolymer has 5 wt% to 15 wt% ethylene.

[0250] Embodiment D The lubricating oil composition of embodiment A, wherein the copolymer has 6 wt% to 12 wt% ethylene.

[0251] Embodiment E The lubricating oil composition of embodiment A, wherein the copolymer has 7 wt% to 9 wt% ethylene.

[0252] Embodiment F The lubricating oil composition of any one of embodiments A to E, wherein the copolymer has 60% to 90% rr triads.

[0253] Embodiment G The lubricating oil composition of any one of embodiments A to F, wherein the copolymer has 70% to 90% rr triads.

[0254] Embodiment H The lubricating oil composition of any one of embodiments A to G, wherein the copolymer has 80% to 90% rr triads.

[0255] Embodiment I The lubricating oil composition of any one of embodiments A to H, wherein the ethylene-propylene copolymer based on syndiotactic propylene does not show a distinct melting peak, wherein the peak has a heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10 °C / min.

[0256] Embodiment J The lubricating oil composition of any one of embodiments A to I, wherein the ethylene-propylene copolymer based on syndiotactic propylene is present in the lubricating oil composition at 0.01 wt% to 20 wt%.

[0257] Embodiment K The lubricating oil composition of any of embodiments A to J, wherein the lubricant base oil has a kinematic viscosity at 100°C of 1.4 to 20.0 mm 2 / s.

[0258] Embodiment L The lubricating oil composition of any of embodiments A to K, wherein the lubricating oil composition has a kinematic viscosity at 100°C of 3.0 to 30.0 mm 2 / s.

[0259] Embodiment M The lubricating oil composition of any of embodiments A to L, wherein the lubricant base oil is a high purity mineral base oil, a gas to liquid (GTL) base oil, an ester base oil, or a synthetic lubricant base oil, which has been classified as a Group I oil, a Group II oil, a Group III oil, a Group IV oil, or a Group V oil, or a blend thereof.

[0260] Embodiment N The lubricating oil composition of any of embodiments A to M, further comprising at least one of a dispersant, a detergent, an antioxidant, a pour point depressant, a friction modifier, a wear modifier, an extreme pressure additive, an antifoam agent, a demulsifier, or a corrosion inhibitor.

[0261] Embodiment O A method of making a lubricating oil composition, comprising mixing a lubricant base oil and a viscosity index improver, wherein the viscosity index improver comprises an ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 wt% to 20 wt% of ethylene; b) 80 wt% to 98 wt% of propylene; c) 50% to 99% of rr triads; and d) 10 kg / mol to 250 kg / mol of Mw(LS);

[0262] Embodiment P The method of embodiment O, wherein the copolymer has 5 wt% to 15 wt% of ethylene.

[0263] Embodiment Q The method of any of embodiments O or P, wherein the copolymer has 60% to 90% of rr triads.

[0264] Embodiment R The method of any of embodiments O to Q, wherein the ethylene-propylene copolymer based on syndiotactic propylene does not show a distinct melting peak, wherein the peak has a melting heat of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10 °C / min.

[0265] Embodiment S The method of any of embodiments O to R, wherein the lubricant base oil further comprises at least one of a dispersant, a detergent, an antioxidant, a pour point depressant, a friction modifier, a wear modifier, an extreme pressure additive, an antifoam agent, a demulsifier, or a corrosion inhibitor.

[0266] Embodiment T The method of any of embodiments O to S, wherein the lubricant base oil has a kinematic viscosity at 100°C of 1.4 to 20.0 mm 2 / s and is a high purity mineral base oil, a gas to liquid (GTL) base oil, an ester base oil, or a synthetic lubricant base oil that has been classified as a Group I oil, a Group II oil, a Group III oil, a Group IV oil, or a Group V oil, or a blend thereof.

[0267] Embodiment U A method of lubricating an engine comprising: supplying to the engine a lubricating oil composition comprising: a major amount of a base oil of lubricating viscosity; and an ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 wt% to 20 wt% ethylene; b) 80 wt% to 98 wt% propylene; c) 50% to 99% rr triads; and d) 10 kg / mol to 250 kg / mol Mw(LS).

[0268] Embodiment V The method of embodiment U, wherein the copolymer has 5 wt% to 15 wt% ethylene.

[0269] Embodiment W The method of either of embodiments V or U, wherein the copolymer has 60% to 90% rr triads.

[0270] Embodiment X The method of any of embodiments U to W, wherein the ethylene-propylene copolymer based on syndiotactic propylene shows no distinct melting peak, wherein the peak has a heat of fusion of 5 J / g or less as determined by differential scanning calorimetry (ASTM D3418-03) at a scan rate of 10 °C / min.

[0271] Embodiment Y The method of any of embodiments U to X, wherein the lubricating oil composition further comprises at least one of a dispersant, a detergent, an antioxidant, a pour point depressant, a friction modifier, a wear modifier, an extreme pressure additive, an antifoam agent, a demulsifier, or a corrosion inhibitor.

[0272] In one embodiment, the lubricating oil composition of the present disclosure can be identified by the Society of Automotive Engineers (SAE) viscosity standards for automotive lubricants. For example, the lubricating oil composition can be identified by the SAE J300 standard (Viscosity Classification of Engine Oils). The J300-2015 viscosity grades are the most recent guidelines of the SAE.

[0273] When the lubricating oil composition comprises one or more of the components discussed above, the additives are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table A below.

[0274] Table A

[0275]

[0276] Examples

[0277] The syndiotactic ethylene-propylene copolymers were made in a continuous solution polymerization process. The polymerization of the examples listed in Tables 1 and 2 were carried out in a continuous stirred tank reactor system. A 1 liter autoclave reactor was equipped with an agitator, a pressure controller, and a water-cooled / steam-heated element with temperature controller. The reactor was operated in a liquid-filled state with the reactor pressure exceeding the bubble point pressure of the reactant mixture, so that the reactants were in the liquid phase. Isobutane and propylene were pumped into the reactor by a Pulsa feed pump. Ethylene and H2 flowed as gases through Brooks flow controllers. The ethylene, propylene, and H2 feed streams were combined into one stream, which was then mixed with a pre-cooled isobutane stream cooled to at least 0°C. The mixture was then fed to the reactor through a single line. A scavenger solution (a solution of tri-n-octylaluminum (TNOA) in isobutane (25 wt% in hexane, Sigma Aldrich)) was also added to the combined solvent and monomer stream before entering the reactor to further reduce catalyst poisons. A catalyst solution was fed into the reactor through a separate line using an ISCO syringe pump. Isobutane (used as solvent) and monomers (e.g., ethylene and propylene) were purified on an alumina molecular sieve bed. The toluene used to make the catalyst solution was also purified by the same technique.

[0278] The polymer produced in the reactor was discharged through a back pressure control valve, which reduced the pressure to atmospheric pressure. This caused the unconverted monomers in the solution to flash to the gas phase, which was discharged from the top of a gas-liquid separator. The liquid phase, which comprised primarily polymer and solvent, was collected for polymer recovery. The collected sample was first air-dried in a fume hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours. The vacuum oven-dried sample was weighed to obtain the product.

[0279] For Examples #1 to #5 listed in Table 1, diphenylmethylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (Catalyst #1) was used as the catalyst with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate as the activator. Bis(p-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (Catalyst #2) was used as the catalyst in Examples #13 to #22 (listed in Table 2). N,N-dimethylanilinium tetrakis(sept-fluoro-2-naphthyl)borate was used as the activator for Examples #17 to #19 and #22. N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was used as the activator for Examples #13 to #16 and #20 to #21. All catalysts were pre-activated with the activator in a 1 : 1 molar ratio in toluene. The reactor pressure for all examples was 350 psig. The detailed process conditions and some characterization data are summarized in Tables 1 and 2. The structures of Catalyst #1 and Catalyst #2 are as follows:

[0280]

[0281] Table 1

[0282]

[0283] Table 2

[0284]

[0285] Table 2 (continued)

[0286]

[0287] Table 3 Polymerizations for Examples #6 to #12 listed in Table 3 were conducted in a 28 liter continuously stirred tank reactor (autoclave reactor) using a solution process. The autoclave reactor was equipped with an agitator, pressure controller, and insulation to prevent heat loss. The reactor temperature was controlled by controlling the catalyst feed rate and heat was removed by feed cooling. All solvents and monomers were purified over alumina molecular sieve beds. The reactor was operated full of liquid with a pressure of 1600 psig. Isohexane was used as the solvent. It was pumped into the reactor using a turbine pump and its flow rate was controlled by a downstream mass flow controller. Compressed liquefied propylene feed was controlled by a mass flow controller. Hydrogen (if used) was fed to the reactor through a thermal mass flow controller. Ethylene feed was also controlled by a mass flow controller. Ethylene, propylene, and hydrogen (if used) were mixed in isohexane vapor through a manifold at different addition points. A 3 wt% mixture of tri-n-octylaluminum in isohexane was also added through a separate line to the manifold (used as a scavenger), and the combined mixture of monomers, scavenger, and solvent was fed to the reactor through a single line.

[0288] The catalyst used to conduct the polymerization for Examples #6 through #12 was bis(p- triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconium dimethyl (Catalyst #2). The catalyst was pre-activated with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in a 4 liter toluene solution in a 1 : 1 molar ratio. After the solids were dissolved, the solution was pumped into an ISCO pump, which was then dosed into the reactor under agitation. The reactor product stream was treated with a trace amount of methanol to stop the polymerization. The mixture was then separated from the solvent by low pressure flash and then extruded through a devolatilization die. The dried polymer was then pelletized. TM 1076treated, and then devolatilized and extruded. The dried polymer was then pelletized.

[0289] Table 3

[0290]

[0291]

[0292] Table 3 (continued)

[0293]

[0294]

[0295] Specifically, the TE, SSI, and TE / SSI ratio values for Examples 1-15, 17-19, and 22 as viscosity modifiers for lubricating oils were tested. Discussion of TE (including measurement method) can be found in U.S. Patent No. 8,105,992, which is incorporated herein by reference. In particular, thickening efficiency (TE) is a relative measure of a polymer’s ability to thicken an oil, defined as: TE = 2 / c x ln((kv(polymer + oil)) / kvoil) / ln(2), where c is the concentration of the polymer, and kv is the kinematic viscosity at 100°C according to ASTM D445. Shear stability index (SSI) is an indicator of a polymer’s resistance to permanent mechanical shear degradation in an engine. SSI is determined by passing a polymer-oil solution through a high shear Bosch diesel injector 30 times according to the procedure outlined in ASTM D6278. The TE and SSI of the polymer samples herein were determined by dissolving in a Group I diluent oil to a concentration that produced a viscosity of about 15 cSt at 100°C (ASTM D445).

[0296] For comparison, Comparative Example A has an ethylene content of 48 wt%, a TE of 1.93, a SSI of 29.2, a Mw of 54,954 g / mol, a Mw / Mn of 1.85, and a TE / SSI of 0.066. It is clear that the inventive materials have demonstrated a wide range of TE and SSI suitable for use as viscosity modifiers with an improved TE / SSI ratio relative to Comparative Example A.

[0297] Table 4 summarizes the low temperature performance of 5W-30 lubricating oils formulated with the syndiotactic based propylene ethylene-propylene copolymers listed in Examples 1-12 and Comparative Example A. Formulations Fl-Fl 2 and a comparative formulation (F13) were prepared as follows: the same base formulation was combined with 9.5% polymer concentrates made with the inventive syndiotactic based propylene ethylene-propylene copolymers listed in Examples 1-12 and Comparative Example A) to form 5W-30 lubricating oils. These 5W30 oils all contained the same 7.65% high performance package of additives including dispersants and inhibitors, pour point depressants, and a 65 / 35 balance of 4 and 6 cSt Group III diluent oils. The results show that formulations containing the inventive syndiotactic based propylene ethylene-propylene copolymers performed better in the pour point test than formulations containing Comparative Example. Specifically, the previous discussion has indicated that high pour points in lubricating engine oils can cause temporary interruptions in oil flow, thereby increasing bearing wear. For modern engine oil grades such as 5W-30, it is desirable to avoid pour points higher than -35°C. The overall balanced performance to meet SAE J300 requirements makes the inventive examples ideal viscosity modifier candidates for lubricating oil applications. The tests were conducted according to the following protocols: pour point (ASTM D-97), CCS (ASTM D-5293), and MRV (ASTM D-4684).

[0298] Table 4

[0299] Formulation F1 F2 F3 F4 F5 F6 Copolymer, example 1 2 3 4 5 6 Ethylene content, wt% 7.9 9.6 7.9 4.8 5.7 7.7 Kinematic viscosity (100°C), mm 2 / s]]> 10.34 10.34 10.27 10.69 10.34 10.4 CCS viscosity (-30°C), mPa.s 3799 3863 3727 3628 3803 4688 MRV (-35°C) viscosity, mPa.s 16400 17300 16600 20100 20200 19900 MRV (-35°C) yield stress, Pa ＜35 ＜35 ＜35 ＜35 ＜35 ＜35 Pour point, °C -39 -39 -42 -42 -42 -39

[0300] Table 4 (continued)

[0301]

[0302] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any lower-limited range can be combined with any upper limit to record an unspecified range, and any lower-limited range can be combined with any other lower limit to record an unspecified range, and similarly, any upper-limited range can be combined with any other upper limit to record an unspecified range. In addition, a range includes every point or individual value between its endpoints, even if not explicitly stated. Thus, every point or individual value can serve as its own lower limit or upper limit, combined with any other point or individual value, or any other lower limit or upper limit, to record an unspecified range.

[0303] As used herein, the term "major amount" refers to an amount of 50% or greater, while the term "minor amount" refers to less than 50%. In addition, when amounts and percentages are given, unless otherwise indicated, it should be understood that they refer to weight.

[0304] Unless otherwise indicated, the phrase "consisting essentially of" does not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in the specification, as long as these steps, elements, or materials do not affect the basic and novel characteristics of the disclosure, and further, they do not exclude impurities and variances normally associated with the elements and materials used.

[0305] Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever the transitional phrase “comprising” is used before a composition, element, or group of elements, it should be understood that we also contemplate the same composition, element, or group of elements preceded by the transitional phrase “consisting essentially of,” “consisting of,” “selected from the group consisting of,” or “is,” and vice versa.

[0306] As used herein, the terms "a" and "the" are to be construed as including the plural as well as the singular.

[0307] Unless otherwise stated, room temperature is approximately 23°C.

[0308] The term "continuous" refers to a system that operates without interruption or cessation. For example, a continuous process for producing polymers means that during the polymerization process, reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0309] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or otherwise by the persons in the pertinent art at the time of the filing date of this application. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0310] The foregoing description of the present disclosure has been presented for the purposes of illustration and description. Furthermore, the disclosure is only illustrative of preferred embodiments and is not intended to be limiting of the disclosure. As will be readily appreciated by one skilled in the art, the present disclosure is capable of being practiced with multiple other combinations, modifications and environments and is capable of being practiced or being carried out in various ways beyond those explicitly described herein. Although the foregoing has been described in some detail for purposes of clarity, it should be apparent that certain changes and modifications will be obvious to one skilled in the art and that the various embodiments described herein can be adapted to various situations and applications without departing from the general scope and ambit of the disclosure. Although the foregoing is directed to embodiments of the disclosure, other and further embodiments can be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

[0311] The embodiments described herein are further intended to explain the best modes presently known of practicing the disclosure and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with such modifications as are suited to the particular situation or application or uses. Accordingly, the description is not intended to limit the disclosure to the form disclosed herein. Also, it is intended that the appended claims be construed to include alternative embodiments.

Claims

1. A lubricating oil composition comprising: a major amount of a lubricant base oil; and A minor amount of a viscosity index improver comprising a syndiotactic propylene-based ethylene-propylene copolymer having: a) 2 to 20% by weight of ethylene; b) 80% to 98% by weight of propylene; c) 50% to 99% rr triplets; and d) Mw measured by light scattering of 10 to 250 kg / mol.

2. The lubricating oil composition of claim 1, wherein the copolymer has 4 to 18 wt% ethylene.

3. The lubricating oil composition of claim 1, wherein the copolymer has 5 to 15 weight percent ethylene.

4. The lubricating oil composition of claim 1, wherein the copolymer has 6 to 12 wt% ethylene.

5. The lubricating oil composition of claim 1, wherein the copolymer has 7 to 9 wt% ethylene.

6. The lubricating oil composition of claim 1, wherein the copolymer has 60% to 90% rr triads.

7. The lubricating oil composition of claim 1, wherein the copolymer has 70% to 90% rr triads.

8. The lubricating oil composition of claim 1, wherein the copolymer has 80% to 90% rr triads.

9. The lubricating oil composition according to claim 1, wherein the syndiotactic propylene-based ethylene-propylene copolymer does not show a clear melting peak, wherein the heat of melting as measured by differential scanning calorimetry according to ASTM D3418-03 at a scanning rate of 10°C / min is 5 J / g or less.

10. The lubricating oil composition according to claim 1, wherein the syndiotactic propylene-based ethylene-propylene copolymer is present in the lubricating oil composition at 0.01 wt% to 20 wt%.

11. The lubricating oil composition according to claim 1, wherein the kinematic viscosity of the lubricant base oil at 100°C is 1.4 mm 2 / s to 20.0mm 2 / s.

12. The lubricating oil composition according to claim 1, wherein the kinematic viscosity of the lubricating oil composition at 100°C is 3.0 mm 2 / s to 30.0mm 2 / s.

13. The lubricating oil composition of claim 1 , wherein the lubricant base oil is a high purity mineral base oil, a gas-to-fluid base oil, or a synthetic lubricant base oil classified as a Group I oil, a Group II oil, a Group III oil, a Group IV oil, or a Group V oil, or a blend thereof.

14. The lubricating oil composition according to claim 13, wherein the lubricant base oil is an ester base oil.

15. The lubricating oil composition of claim 1, further comprising at least one of a dispersant, a detergent, an antioxidant, a pour point depressant, a friction modifier, a wear modifier, an extreme pressure additive, a defoamer, a demulsifier, or a corrosion inhibitor.

16. A method for preparing a lubricating oil composition, comprising: A lubricant base oil and a viscosity index improver are mixed, wherein the viscosity index improver comprises: An ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 to 20% by weight of ethylene; b) 80% to 98% by weight of propylene; c) 50% to 99% rr triplets; and d) Mw measured by light scattering of 10 to 250 kg / mol.

17. The method of claim 16, wherein the copolymer has 5 to 15 weight percent ethylene.

18. The method of claim 16, wherein the copolymer has 60% to 90% rr triads.

19. The method of claim 16, wherein the syndiotactic propylene-based ethylene-propylene copolymer does not show a distinct melting peak, wherein the heat of melting as measured by differential scanning calorimetry according to ASTM D3418-03 at a scanning rate of 10°C / min is 5 J / g or less.

20. The method of claim 16, wherein the lubricating oil composition further comprises at least one of the following: Dispersants, detergents, antioxidants, pour point depressants, friction modifiers, wear modifiers, extreme pressure additives, defoamers, demulsifiers, or corrosion inhibitors.

21. The method according to claim 16, wherein the kinematic viscosity of the lubricant base oil at 100°C is 1.4 mm 2 / s to 20.0mm 2 / s, and is a high purity mineral base oil, gas-to-fluid base oil, or synthetic lubricant base oil that has been classified as a Group I oil, a Group II oil, a Group III oil, a Group IV oil, or a Group V oil, or a blend thereof.

22. The method of claim 21, wherein the lubricant base oil is an ester base oil.

23. A method of lubricating an engine, comprising: A lubricating oil composition is supplied to the engine, the lubricating oil composition comprising: a major amount of a base oil of lubricating viscosity; and An ethylene-propylene copolymer based on syndiotactic propylene having: a) 2 to 20% by weight of ethylene; b) 80% to 98% by weight of propylene; c) 50% to 99% rr triplets; and d) Mw measured by light scattering of 10 to 250 kg / mol.

24. The method of claim 23, wherein the copolymer has 5 to 15 weight percent ethylene.

25. The method of claim 23, wherein the copolymer has 60% to 90% rr triads.

26. The method of claim 23, wherein the syndiotactic propylene-based ethylene-propylene copolymer does not show a distinct melting peak, wherein the heat of melting as measured by differential scanning calorimetry according to ASTM D3418-03 at a scanning rate of 10°C / min is 5 J / g or less.

27. The method of claim 23, wherein the lubricating oil composition further comprises at least one of the following: Dispersants, detergents, antioxidants, pour point depressants, friction modifiers, wear modifiers, extreme pressure additives, defoamers, demulsifiers, or corrosion inhibitors.

Images